Water based window glass and chrome cleaner composition

ABSTRACT

A water based cleaning composition including a major portion of water, a minor portion of a cleaning agent such as ammonium hydroxide or a lower alcohol such as isopropanal and a small portion of a polyethylene and alkoxy polyethylene glycol of high molecular weight and triethylene glycol which not only acts as a lubricant but has a preferential affinity for glass and the like as compared with oil, grease, dirt and/or lubricity component such as ammonium bicarbonate or ammonium carbonate.

This application is a continuation-in-part of applicant's copending U.S. application Ser. No. 885,311 filed Mar. 10, 1978, now U.S. Pat. No. 4,213,873.

BACKGROUND

This invention is directed to new and novel highly efficient liquid compounds for cleaning of glass and the like and the method for making same. While principally aimed at the cleaning of windows, mirrors and other objects made of glass, these compounds have been found to be equally useful for the cleaning of polished chromium, stainless steel, porcelain enamels, ceramic, plastics and many other such items that may need to be cleaned of oil, grease, dirt and other contaminants in a similar manner.

Typical liquid type window cleaners presently on the market utilize a water based system, usually combined with solvents such as isopropyl alcohol, butyl cellosolve (2-butoxy ethanol) and the like, to which is added a highly efficient surfactant.

In addition, most such formulations also contain a percentage of ammonia, plus perhaps a phosphate of other such substance, to further enhance grease cutting action.

Special care is taken in the compounding of such formulations to achieve a good balance between evaporation rate of the cleaner applied to the glass and absorption rate into the toweling. Any solids included, such as phosphates, must be limited in amount so as not to leave an objectionable residue on the glass surface. Of particular importance is the achievement of good lubricity so as to reduce the physical effort required by the user during the wiping and drying process as much as possible.

U.S. Pat. No. 3,463,735 issued to Stonebraker and Wise, Aug. 26, 1969, covers such a glass cleaning composition and appears to be typical, with minor variations, of most of the window cleaning liquids presently available on the market going under such trade names as WINDEX, GLASS PLUS, EASY-OFF, AJAX window cleaner, and the like.

The basic principle of operation of these prior art window cleaners is to thoroughly emulsify the oil and grease with the water based cleaning solution, along with loosening any dirt and other contamination. This oil, grease and dirt laden solution is then hopefully wiped from the glass by means of the paper towel or cloth used to wipe the surface dry.

In actuality, it is extremely difficult to thoroughly clean the glass in this manner. Oil and grease, in particular, are difficult to transfer completely to the toweling and at least a portion of the contamination invariably becomes redistributed on the glass as a re-adhering film. The result is the oil and grease streaked window or mirror that almost everyone has experienced with these liquid type cleaners after thinking that a thorough cleaning job had been done.

SUMMARY OF THE INVENTION

The present invention is based on an entirely different principle. It has been found that one of several organic compounds, selected from a closely related group of compounds, can be added to a water based cleaning solution and provide a pronounced affinity for glass and many other surfaces, while at the same time having a definite non-affinity for oil and grease. The cleaning solution may also contain suitable amounts of alcohol, ammonia, surfactants, etc.

More specifically, I have found that a very small percentage of a polyethylene glycol or methoxypolyethylene glycol (condensation polymers of ethylene glycol) introduced into a suitable liquid cleaning solution, and applied for example, to a smooth glass surface, will produce a very thin, visually transparent, well adhering and very smooth and slick coating on the surface of the glass following the wiping and drying operation with paper, cloth, or other type of absorbent toweling. Furthermore, the contaminants loosened by the cleaning liquid, including emulsified oil and grease, have been found to be effectively repelled by the coated glass and transferred almost entirely to the toweling, leaving the glass in an exceptionally clean and streak-free condition.

It has also been found that the thin polyethylene or methoxypolyethylene glycol coating that is formed on the glass surface as a result of the cleaning operation, can effectively repel many airborne organic contaminants such as oil and plasticizer fumes. For example, its use has been found to keep the inside windows in an automobile visually "cleaner" for considerably longer periods of time than any of the several prior art liquid window cleaning solutions that have been run in direct comparison tests.

The molecular weight range for the polyethylene or methoxypolyethylene glycols as used in this invention can be varied considerably. To date, I have used successfully such compounds ranging from 400 to 20,000 in molecular weight and it is believed that even higher molecular weight ranges would be useful, if available.

A typical long chain polyethylene glycol molecule can be represented in the following manner. It can be seen that it contains a large number of oxygen atoms compared with the number of carbon atoms for an organic compound. Also, unlike compounds such as sugars, it contains very few OH groups. The following is representative of a 6,000 molecular weight polyethylene glycol, n ˜130.

    HOCH.sub.2 (CH.sub.2 OCH.sub.2).sub.n CH.sub.2 OH          Formula (1)

The general formula for these compounds is represented by ROCH₂ (CH₂ OCH₂)_(n) CH₂ OR, wherein R is hydrogen or alkyl.

Methoxypolyethylene glycol can be represented as above except that the HO group at each end is replaced with an H₃ C--O-- group.

The non-bonded oxygen electron pairs are apparently strongly attracted to the cations present in the glass or other surface to which an attachment seems to occur.

It is believed that the criteria for the selection of an effective polyethylene glycol like compound as used in this invention can be summarized as follows:

(a) Must have a large number of oxygen atoms per molecule compared to the number of carbon atoms.

(b) Must have a very limited number of hydroxy (OH) groups per molecule.

(c) Must be water soluble.

(d) Must have no chemical reaction with water.

While there may be a few other compounds that satisfy the above criteria, such as polyester or polyamide made from a low molecular weight monomer, the polyethylene and methoxypolyethylene glycols are undoubtedly the most stable, most water soluble, readily available, lowest cost and harmless compounds that have been found in this limited category.

It is not known whether the polyethylene or methoxypolyethylene glycol layer is formed immediately upon application of the relatively dilute solution of the liquid cleaner to the glass or whether it forms its attachment and oil and grease repelling film when it is nearly dry or perhaps even completely dry. In any event, it has been found to cause extremely efficient transfer of the oil or grease into the paper towel or cloth without leaving streaks on the glass. If a streak is inadvertently left on the glass by letting the solution dry before wiping thoroughly, it can still be easily removed by wiping lightly with a dry cloth or paper towel. This indicates that the polyethylene or methoxypolyethylene glycol layer has formed an attachment to the glass underneath the oil or grease contamination layer.

It should be noted that the weight amounts listed in the various tables of this application for polyethylene glycol and methoxypolyethylene glycol may also include an amount of added water. The molecular weight grades of these materials that are solids at room temperature were premixed with water for ease of handling and to assure rapid blending with the liquid cleaner formulations. The amount of water included, if any, in each instance is set forth by the notes referred to in each table. In summary, the weight values listed for polyethylene glycol 400 and methoxypolyethylene glycol 550 are correct as listed in the tables and include no water. The weights given for polyethylene glycol 1,540, 4,000 and 6,000 and for methoxypolyethylene glycol 2,000 and 5,000 include 1 part water and 1 part glycol by weight. The weight for the polyethylene glycol 20,000 linear and polyethylene glycol compound 20M includes 2 parts water to 1 part of the glycol by weight. The weights for these materials referenced in the claims are without added water. The notes referred to in each table are set forth for the first time in Table I.

Examples of some basic liquid window and glass cleaning formulations according to the invention have been presented in Table I to provide a better overall idea of the invention.

                                      TABLE I                                      __________________________________________________________________________     BASIC FORMULATION EXAMPLES                                                                                Or-                                                                            ganic                                                                          Lu-                    Polyethylene or                                         bri-                   Methoxypoly-                   Water &                                                                               Amount                                                                              Grease Cutting                                                                         Amount                                                                              cant                                                                               Amount        Amount                                                                              ethylene                                                                               Amount               # Alcohol                                                                               (grams)                                                                             Aids    (grams)                                                                             Aids                                                                               (grams)                                                                             Surfactant                                                                              (grams)                                                                             Glycol  (grams)              __________________________________________________________________________     1 H.sub.2 O                                                                             100  NH.sub.4 OH.sup.(o)                                                                    0.312                                                                               --  --   --       --   PEG-6K.sup.(h)                                                                         0.10                 2 H.sub.2 O                                                                             80    --     --   --  --   --       --   PEG-6K.sup.(h)                                                                         0.08                   Isopropanol                                                                           15.70                                                                 3 H.sub.2 O                                                                             90.80                                                                               NH.sub.4 OH.sup.(o)                                                                    0.364                                                                               --  --   --       --   MPEG-5K.sup.(f)                                                                        0.20                   Isopropanol                                                                           2.35                                                                    1-propanol                                                                            4.05                                                                  4 H.sub.2 O                                                                             88.65                                                                               NH.sub.4 OH.sup.(o)                                                                    0.260                                                                               --  --   NEKAL BA-77.sup.(b)                                                                     0.011                                                                               MPEG-2K.sup.(n)                                                                        0.182                  Isopropanol                                                                           3.15                                                                    1-propanol                                                                            4.90                                                                  5 H.sub.2 O                                                                             90.80                                                                               KBO.sub.2 .  × H.sub.2 O                                                         0.10 2,3-bu-                                                                            0.039                                                                               NEKAL BX-78.sup.(c)                                                                     0.007                                                                               PEGC-20M.sup.(i)                                                                       0.26                   Isopropanol                                                                           2.35 NH.sub.4 HCO.sub.3                                                                     0.10 tane-                                                 1-propanol                                                                            4.05              diol                                                6 H.sub.2 O                                                                             86.75                                                                               NH.sub.4 OH.sup.(p)                                                                    0.156                                                                               2,3-bu-                                                                            0.039                                                                               NEKAL BX-78.sup.(c)                                                                     0.007                                                                               PEGC-20M.sup.(i)                                                                       0.26                   Isopropanol                                                                           9.45              tane-                                                 1-propanol                                                                            0.247             diol                                                __________________________________________________________________________      .sup.(b) NEKAL surfactant, sodium alkylnaphthalene sulfonate, Mfg, by GAF      Corporation, New York, N.Y.                                                    .sup.(c) NEKAL surfactant, sodium alkylnaphthalene sulfonate, Mfg. by GAF      Corporation, New York, N.Y.                                                    .sup.(f) Carbowax methoxypolyethylene glycol, 5000 molecular weight, Mfg.      by Union Carbide Corporation, New York, N.Y. Amount shown includes             MPEG5000 + H.sub.2 O 1:1 by weight                                             .sup.(h) Carbowax polyethylene glycol, 6000-7500 molecular weight, Mfg. b      Union Carbide Corporation, New York, N.Y. Amount shown includes PEG6000 +      H.sub.2 O 1:1 by weight                                                        .sup.(i) Polyethylene Glycol Compound20M, approx. molecular weight of          15,000, Mfg. by Union Carbide Corporation, New York, N.Y. Amount shown         includes PEGC20M + H.sub.2 O 1:2 by weight                                     .sup.(n) Carbowax methoxypolyethylene glycol, 1900 molecular weight, Mfg.      by Union Carbide Corporation, New York, N.Y. Amount shown includes             MPEG2000 + H.sub.2 O 1:1 by weight                                             .sup.(o) 28% NH.sub.3                                                          .sup.(p) 30% NH.sub.3                                                    

Formulation 1 shows a mixture of water, polyethylene glycol and ammonia. While admittedly a very simple composition, such a cleaning solution is found useful for application to windows with a sponge or similar means and then removing the liquid with a squeegee. Other grease cutting additives such as phosphates, borates, glyconates, citrates, etc., could of course be included with or without the ammonia. The example does, however, illustrate the very small percentage of polyethylene glycol that can be used in such applications.

The remaining formulations in Table I show cleaning solutions intended to be applied to the glass or other smooth surface by spray or similar means and then wiping from the surface by absorbent toweling. The various additives in these examples are included for such purposes as improved grease cutting, adjustment of absorbency rate into toweling, maximizing lubricity during the wiping dry operation and varying the evaporation rate of the cleaner.

The alcohol used in formulations 2, 3, 4, 5 and 6 of Table I, aids in several ways: (1) it substantially improves the lubricity during the wiping operation with the toweling; (2) it helps dissolve and emulsify oil and grease films that may be present on the glass or other surface; (3) it speeds evaporation of the cleaning liquid; and, (4) increases the wicking rate into the toweling due to its inherent wetting properties.

The ammonia included in most of these formulations (1, 2, 3, 4 and 6) helps to saponify any contaminating oils and greases. It has the special advantage that it evaporates completely, leaving no residue on the glass or other surface being cleaned.

Formulations 3, 4, 5 and 6 have a combination of alcohols. These have been found to provide greater lubricity (less drag) during the wiping dry operation than either alcohol alone.

Formulations 4, 5 and 6 all contain a surfactant or surface active agent. In these particular examples, a sodium alkanapthylene sulfonate. This has been added to the solution primarily for its wetting ability and increasing the absorbency rate of the liquid into the toweling. The use of surfactants must be very carefully controlled so as not to effect the oil and grease repelling properties of the polyethylene glycol and methoxypolyethylene glycol additive.

Formulation 5 contains no ammonia but instead makes use of small amounts of soluble solids as grease cutting aids (in this instance potassium metaborate and ammonium bicarbonate). The latter also improves the lubricity to a marked extent and in this respect serves a dual purpose. Small amounts of phosphates, silicates, citrates, etc., can also make effective additives.

Formulation 6 includes 2,3-butanediol as an organic lubricant additive. When used in the correct proportions with the alcohols, such higher boiling point organics can often markedly improve the ease of wiping during the drying operation and make a more frictionless transition between the nearly dry to the completely dry stage.

In accordance with the overall invention, all of these formulations include the polyethylene glycol and/or methoxypolyethylene glycol, as an oil and grease repelling additive. The higher molecular weight grades are hard wax type materials when free of water and other solvents. These grades were selected in these examples so as to impart a very smooth slick surface by the time the cleaning solution is wiped to the completely dry stage.

For more detailed discussions, along with examples of representative formulations and comparative test results, reference is made to the following:

The low boiling point monohydroxy alcohols are commonly used in most all commercially available liquid window and glass cleaning solutions now on the market. The alcohol aids in dissolving or emulsifying oil and grease, can noticeably improve overall lubricity of the cleaner and increase evaporation rates and wicking rates into absorbent toweling. Higher boiling point organic solvents are often also added along with the alcohol to modify some or all of the effects just listed.

These alcohols and other solvents are normally selected to have boiling points that fall within the range of 60° C.-250° C. The higher boiling point limitation is to assure that evaporation is more or less complete by the time the surface has been wiped to a "dry" condition.

U.S. patents covering various window cleaner products, e.g., U.S. Pat. No. 3,839,234 (Oct. 1, 1974) to Roscoe; U.S. Pat. No. 2,993,866 (July 25, 1961) to Vaughn, et al; U.S. Pat. No. 3,679,609 (July 25, 1972) to Castner; U.S. Pat. No. 3,696,043 (Oct. 3, 1972) to Labarge et al; U.S. Pat. No. 2,386,106 (Oct. 2, 1945) to Gangloff, and the patent mentioned earlier, U.S. Pat. No. 3,463,735 (Aug. 26, 1969) to Stonebraker and Wise, are cases in point where one or more alcohols or organic solvents are included in a liquid window or glass cleaner formulation.

The addition of one or more of the low molecular weight, low boiling point monohydroxy alcohols, including methanol, ethanol, isopropanol and 1-propanol, have been found to be advantageous for use in the present invention.

All four of these alcohols are helpful in achieving desirable evaporation rates, wicking rates into the toweling and aid in loosening and emulsifying oil, grease and other contaminating films on the surface being cleaned.

The major difference between the alcohols for use in the various formulations of this invention, has been found to be their effect on overall lubricity. By this is meant the ease with which the surface being cleaned can be wiped with suitable absorbent toweling from the initial wet stage, through the intermediate stages to the final completely dry stage.

In this respect, the isopropanol and 1-propanol are found to provide the highest degree of lubricity when used individually and in sufficient amount. The methanol provided the least lubricity improvement and the ethanol assumes an intermediate position.

These comparisons, using ˜10% alcohol to water content by weight are shown in the data of Table II. The overall formulation used in this test was fairly basic in nature. Although not shown here, similar tests with other formulations (such as substituting polyethylene glycol for the methoxypolyethylene glycol and omitting the 2,3-butanediol) and using different alcohol percentages, have shown the same basic lubricity results for the four alcohols in question.

                                      TABLE II                                     __________________________________________________________________________     EFFECT OF TYPE OF ALCOHOL ADDITIVE ON                                          OVERALL LUBRICITY                                                                                      BASIC FORMULATION:                                                                           86.75g H.sub.2 O                                                                -- Alcohol - see below                                                        0.208g NH.sub.4 OH.sup.(p)                                                     0.026g 2,3-butanediol                                                          0.018g surfactant, BA-77.sup. (b)                                              0.20g MPEG-5K.sup.(f)                                            TEST SURFACE: 24" × 18" Plate Glass                              Boiling                                                                   Amount                                                                              Point                                                                              Lubricity - (Measured in terms of comparative drag                             while wiping                                               #   Alcohol                                                                               (grams)                                                                             (PC)                                                                                    glass surface from wet to dry stage with paper                            towel)                                                     __________________________________________________________________________     BN-31                                                                              Methanol                                                                              9.5  64.5                                                                               More drag nearly dry than BN-32 ˜ BN-32 & BN-33                          when dry                                                   BN-32                                                                              Ethanol                                                                               9.55 78.5                                                                               A little more drag than BN-33 nearly dry ˜                               BN-33 dry                                                  BN-33                                                                              Isopropanol                                                                           9.4  82.3                                                                               Very low drag nearly dry                                   BN-34                                                                              1-propanol                                                                            9.5  97.2                                                                               Slightly more drag nearly dry than BN-33, but also                             slightly less drag                                                             nearly dry than BN-32. Very slightly less drag than                            BN-33 when dry                                             __________________________________________________________________________      NOTES  See Table I                                                       

Alcohols such as the butanols and pentanols have not been considered because of their inherent toxicity, eye irritant properties, or other such disadvantages. Even though included in Table II, the use of ethanol is seriously questioned from a practical standpoint due to government regulations that make its use in a product of this type difficult and somewhat costly.

While methanol provides the poorest lubricity improvement of the alcohols tested, it can still be a viable additive in specialized cases. An example would be for use in low freezing point solutions such as for automatic, automobile windshield washers, etc., where other factors may outweigh that of achieving maximum lubricity.

An interesting finding was that a mixture of isopropanol and 1-propanol can result in a considerable lubricity improvement over that of either alcohol alone. Furthermore, it has been found that there are two different proportions that achieve maximum lubricity, one favoring the 1-propanol as the alcohol having the largest percentage involved and the other favoring the isopropanol. These two systems are shown in Tables III and IV, respectively.

                                      TABLE III                                    __________________________________________________________________________     1-PROPANOL, ISOPROPANOL MIXTURES FOR MAXIMIZING                                LUBRICITY, WITH 1-PROPANOL PREDOMINATING                                                                  BASIC FORMULATION:                                                                           83.75g H.sub.2 O                                                                -- Alcohol - See below                                                        0.364g NH.sub.4 OH.sup.(o)                                                     0.026g 2,3, Butanediol                                                         0.011g surfactant,                                                             BA-77.sup.(b)                                                                  0.20g MPEG-5K.sup.(f)                                            TEST SURFACE: 24" × 18" Plate Glass                          Ratio                                                                     Amount                                                                              1-Propanol:                                                                           Lubricity (Comparative drag while wiping surface                               from wet to dry                                          #  Alcohol                                                                               (grams)                                                                             Isopropanol                                                                                stage with paper towel)                             __________________________________________________________________________                           Noticeably more drag nearly dry than CJ-4 and also                             more completely                                          CJ-1                                                                              Isopropanol                                                                           11.75                                                                               0%     dry                                                                            Slightly lower drag nearly dry than CJ-6 but not                               quite as smooth                                                                completely dry                                              Isopropanol                                                                           9.45                                                                 CJ-2           0.2:1  Note quite as much drag when nearly dry or dry as                              CJ-1                                                        1-propanol                                                                            2.20                                                                    Isopropanol                                                                           7.15                                                                 CJ-3           0.7:1  Less drag nearly dry and dry than CJ-2                      1-propanol                                                                            4.80        Slightly more drag nearly dry and dry than CJ-7             Isopropanol                                                                           5.45                                                                 CJ-7           1.2:1  Very slightly more drag nearly dry and dry than                                CJ-4                                                        1-propanol                                                                            6.50                                                                    Isopropanol                                                                           4.61                                                                 CJ-4           1.6:1  Excellent - Least drag wet to completely dry of any                            formulation in                                              1-propanol                                                                            7.45        test                                                        Isopropanol                                                                           3.90                                                                 CJ-8           2.1:1  ˜CJ-7                                                 1-propanol                                                                            8.15                                                                    Isopropanol                                                                           2.30                                                                 CJ-5           4.3:1  Slightly more drag nearly dry and dry than CJ-8             1-propanol                                                                            9.80        Not quite as much drag as CJ-6                                                 Slightly more drag nearly dry and dry than CJ-5          CJ-6                                                                              1-propanol                                                                            12.1 100%   Slightly drag than CJ-1 nearly dry but very                                    Slightly less drag completely dry                        __________________________________________________________________________      Notes  See Table I                                                       

                                      TABLE IV                                     __________________________________________________________________________     ISOPROPANOL, 1-PROPANOL MIXTURES FOR                                           MAXIMIZING LUBRICITY WITH ISOPROPANOL                                          PREDOMINATING                                                                                            BASIC FORMULATION:                                                                           90.85g                                                                             H.sub.2 O                                                                  --  Alcohol - see below                                                        0.104g                                                                             NH.sub.4 OH.sup.(p)                                                        0.10g                                                                              K.sub.4 B.sub.2 O.sub.7 .                                                      4H.sub.2 O                                                                 0.10g                                                                              NH.sub.4 HCO.sub.3                                                         0.018g                                                                             Surfactant, BA-77.sup.(b)                                                  0.20g                                                                              MPEG-5K.sup.(f)                                    Ratio                                                                     Amount                                                                              Isopropanol:                                                                          Lubricity (Comparative drag while wiping surface                               from wet to dry                                         #   Alcohol                                                                               (gram)                                                                              1-Propanol                                                                                 stage with paper towel)                            __________________________________________________________________________     JB-1                                                                               Isopropanol                                                                           6.10 100%   Considerably more drag nearly dry and a little                                 more drag completely                                                           dry than JB-20 and JB-22                                    Isopropanol                                                                           6.10        Noticeably less drag nearly dry and dry than JB-1       JB-20A          52.6:1 Definitely more drag nearly dry than JB-20 and                                 JB-22                                                       1-propanol                                                                            0.116       but ˜ same completely dry                             Isopropanol                                                                           6.10                                                                JB-20           42.1:1 Excellent - Same as JB-22 - Least drag wet to                                  completely dry in                                           1-propanol                                                                            0.145       test                                                        Isopropanol                                                                           6.10                                                                JB-22           38.1:1 Excellent - Same as JB-20 - Can't tell difference           Isopropanol                                                                           0.160                                                                   Isopropanol                                                                           6.10                                                                JB-21           35.1:1 Very slightly more drag nearly dry than JB-20 and                              JB-22                                                       1-propanol                                                                            0.174       But ˜ same completely dry                             Isopropanol                                                                           6.10                                                                JB-20B          30.1:1 Definitely more drag than JB-20 and JB-22                   1-propanol                                                                            0.203       Nearly dry but ˜ same completely dry                  Isopropanol                                                                           2.35        A little more drag nearly dry than JB-20 and                                   JB-22                                                   JB-2            0.6:1  But ˜ same completely dry. Definitely less                               drag                                                        1-propanol                                                                            4.05        than JB-20A and JB-20B nearly dry and ˜ same                             completely                                                                     dry                                                     __________________________________________________________________________      Notes  See Table I                                                       

As can be noted from the data in Table III, maximum lubricity has been achieved in formulation CJ-4 with a 1-propanol to isopropanol ratio of the order of 1.6:1 by weight. Table IV, on the other hand, shows that maximum lubricity can also be achieved with a ratio of isopropanol to 1-propanol of ˜40:1, as shown in formulations JB-20 and JB-22.

From a number of different tests, it has been found that the alcohol ratios as used in Table IV, formulation JB-20 and JB-22, where the isopropanol predominates, will provide slightly better lubricity than the proportions of formulation CJ-4 of Table III. Formulation JB-2 with the alcohol proportions maximized with the 1-propanol predominating has been included in Table IV to show lubricity comparisons between the two systems with an otherwise identical composition.

Tables V and VI show the effect of varying the total alcohol to water content from no alcohol to a maximum of ˜20%. As can be seen from these tables, a minimum amount of alcohol below about 4% was found to cause a very noticeable increase in friction and an associated squeeking sound while wiping the glass surface with absorbent toweling from the wet to the partially dry stage.

                                      TABLE V                                      __________________________________________________________________________     EFFECT ON LUBRICITY OF VARYING WATER                                           TO TOTAL ALCOHOL CONTENT USING 1-PROPANOL                                      TO ISOPROPANOL RATIO OF ˜ 1.6:1                                                                        BASIC FORMULATION:                                                                            --  H.sub.2 O - see below                                                      -- Alcohol - see below                                                        0.364g NH.sub.4 OH.sup.(o)                                                     0.026g 2,3-butanediol                                                          0.011g Surfactant                                                              BA-77.sup.(b)                                                                  0.20g MPEG-5K.sup.(f)                                            TEST SURFACE: 24" × 18" Plate Glass                 Iso- l-   %                                                               H.sub.2 O                                                                           propanol                                                                            propanol                                                                            Alcohol                                                                             Lubricity (Comparative drag while wiping with                                  paper towel                                            #   (grams)                                                                             (grams)                                                                             (grams)                                                                             to H.sub.2 O                                                                             from wet to dry stage)                            __________________________________________________________________________     CM-8                                                                               78.60                                                                               6.30 9.80 20.1%                                                                               Excellent - Low drag wet to dry stage                  CM-1                                                                               83.50                                                                               4.65 7.45 14.5%                                                                               ˜CM-8                                            CM-2                                                                               85.70                                                                               4.00 6.30 12.0%                                                                               ˜CM-8                                            CM-3                                                                               88.65                                                                               3.15 4.90 9.1% ˜CM-8                                            CM-4                                                                               90.80                                                                               2.35 4.05 7.1% ˜CM-8                                            CM-5                                                                               93.45                                                                               1.55 2.50 4.3% Drag ˜ CM-8 When wiping in nearly dry to                                 dry stages but just beginning                                                  to squeak when wet                                     CM-7                                                                               95.90                                                                               0.78 1.25 2.1% Squeaks when wet until nearly dry. ˜CM-8                                 when completely dry however                            CM-6                                                                               100.00                                                                              0    0      0% Excessive squeaking ˜ Very difficult to use                              also not as smooth completely                                                  dry as CM-8                                            __________________________________________________________________________      Notes  See Table I                                                       

                                      TABLE VI                                     __________________________________________________________________________     EFFECT ON LUBRICITY OF VARYING WATER TO                                        TOTAL ALCOHOL CONTENT USING ISOPROPANOL                                        TO 1-PROPANOL RATIO OF ˜ 40:1                                                                        BASIC FORMULATION:                                                                            --  H.sub.2 O - see below                                                      -- Alcohol - see below                                                        0.104g NH.sub.4 OH.sup.(p)                                                     0.10g K.sub.4 B.sub.2 O.sub.7 .                                                4H.sub.2 O                                                                     0.10g NH.sub.4 HCO.sub.3                                                       0.018g Surfactant                                                              BA-77.sup.(b)                                                                  0.20g MPEG-5K.sup.(f)                                            TEST SURFACE: 24" × 18" Plate Glass                  Iso- 1-   %                                                               H.sub.2 O                                                                           propanol                                                                            propanol                                                                            Alcohol                                                                             Lubricity (Comparative drag while wiping with                                  paper towel from wet                                    #  (grams)                                                                             (grams)                                                                             (grams)                                                                             to H.sub.2 O                                                                             to dry stage)                                      __________________________________________________________________________     LA-1                                                                              78.65                                                                               15.65                                                                               0.406                                                                               20.4%                                                                               Excellent - Low drag wet to dry stage                   LA-2                                                                              85.90                                                                               10.00                                                                               0.254                                                                               11.9%                                                                               ˜LA-1                                             LA-3                                                                              90.85                                                                               6.10 0.152                                                                               6.9% ˜ LA-1                                                                   A little more drag nearly dry than LA-1, ˜                               LA-1 when dry. -LA-4 93.30 4.00 0.102 4.4% Just on                             verge of squeaking when being wiped in nearly dry                              stage                                                                          More drag nearly dry than LA-4, ˜ LA-1 when                              dry.                                                    LA-6                                                                              95.58                                                                               3.05 0.076                                                                               3.3% Considerably more drag nearly dry than LA-1                                    Some squeaking when wiped in wet to nearly dry                                 stage                                                                          Very bad drag nearly dry, much more than LA-6           LA-5                                                                              100.00                                                                              0    0      0% Very much more than LA-1 nearly dry but ˜                                LA-1 dry.                                               (CM-6)                 Squeaks badly wet to nearly dry.                        __________________________________________________________________________      Notes  See Table I                                                       

The preferred alcoholic content limit is hard to establish solely from a lubricity comparison standpoint as amounts as great as about 50% by weight have been found to provide equivalent lubricity to more moderate amounts as low as about 5% by weight.

In general, it has been found that an alcoholic content in the range of about 7% to about 15% by weight is a good range for most normal window and glass cleaning applications. This range will provide good lubricity as well as suitable wicking, evaporation rates, and oil removal properties. Higher alcoholic content may be required for specialized uses such as for cleaning fluids designed for use during freezing weather. Lower alcoholic content may be desirable in extremely dry and hot climates to slow the evaporation rate.

Higher boiling point, water miscible solvents, such as butyl, ethyl and methyl cellosolve, diethylene glycol, dimethyl ether, carbitol acetate, methoxypropanol, 1,4-butandeiol, etc., can also make useful additives to the cleaning solutions of this invention. For the most part, however, their use has been limited to very small amounts, being included mainly as aids to improving overall lubricity of particular formulations.

The use of larger amounts of such high boiling point water soluble solvents has been found, in general, to slow down evaporative and/or wicking rates to an unacceptable level.

This is unlike many commercial window cleaning formulations where the higher boiler point solvents are often added for the express purpose of slowing the drying rate. This seeming anomoly is undoubtedly due in large part to the highly efficient surfactants, used in many such commercial formulations, that can cause extremely rapid wicking into the toweling. Such highly efficient surfactants and wetting agents cannot be employed in the formulations of this invention, as will be explained later, therefore necessitating, in most instances, the use of the lower boiling point alcohols and limiting the use of the higher boiling point solvents to small amounts.

One of the major goals of this invention has been to produce an improved liquid cleaning solution so that it possesses a high degree of lubricity. That is, minimizing the physical effort required by the user during the wiping operation with the absorbent toweling from the wet to the completely dry stage.

Fortunately, one of the advantages of the use of the polyethylene or methoxypolyethylene glycol in the liquid cleaning solutions of this invention is their lubricating properties. This is especially true for the higher molecular weight polyethylene glycol and methoxypolyethylene glycol compounds that dry as a thin but hard synthetic wax after the liquids have evaporated. The glass or other surface being cleaned becomes particularly smooth and slick when this point is reached.

By the proper use of certain of the higher boiling point organic additives to compliment the alcohols and polyethylene glycols or methoxypolyethylene glycols, a further improvement in overall lubricity can often be achieved during the drying operation with absorbent toweling.

Such additives apparently fill the gap during the period when the alcohol can no longer provide adequate lubricity, (probably due to its evaporation or absorption into the toweling) to the point where the very thin but slick polyethylene glycol and/or methoxypolyethylene glycol surface layer has been established. The latter does not occur until the surface has been wiped to a reasonably dry stage.

It should also be pointed out that some of these higher boiling point organic additives have also been found to increase the final, completely dry, lubricity of the surface. Apparently this is due to the additive causing a more uniform spreading of the polyethylene glycol or methoxypolyethylene glycol during its final drying stage.

Table VII covers examples of a number of these high boiling point organics incorporated in a cleaning solution for the purpose of enhancing the overall lubricity. The basic formulation in this case is similar to that of sample CM-5 of Table V presented earlier except that the 5000 molecular weight methoxypolyethylene glycol has been substituted with polyethylene glycol of the 6,000 molecular weight range. Also, the 2,3-butanediol is replaced with other high boiling point additives except for formulation CP-2 which has been included for lubricity comparison purposes.

                                      TABLE VII                                    __________________________________________________________________________     HIGH BOILING POINT ORGANIC ADDITIVES                                           FOR IMPROVING LUBRICITY IN FORMULATION                                         WHEN ALSO USED WITH ISOPROPANOL AND                                            1-PROPANOL                                                                                                        BASIC FORMULATION:                                                                           93.45g H.sub.2 O                                                               1.55g Isopropanol                                                              2.5g 1-propanol                                                                0.364g                                                                         NH.sub.4 OH.sup.(o)                                                            0.011g Surfactant                                                              BA-77.sup.(b)                                                                  0.20g PEG-6K.sup.(h)                                             TEST SURFACE: 24" × 18" Plate                                                          Glass                                              Boiling                                                       High Boiling Point                                                                        Amount                                                                               Point of                                                                             Lubricity - Through Nearly                                                                       Lubricity - When in Dry           #   Organic Lubricant                                                                         (grams)                                                                              Lubricant                                                                            Dry Stage         Stage                             __________________________________________________________________________                                Considerably more drag than                                                                      Noticeably more drag than         CQ-1                                                                               none       --    --    CQ-2              CQ-2                              CQ-2                                                                               2,3-butanediol                                                                            0.026 187 C Excellent         Excellent                             3-Methoxy                                ˜ CQ-2 but probably                                                      not quite as                      CQ-3                                                                               1-butanol  0.144 161 C ˜ CQ-2      smooth transition nearly dry                                                   to dry                                                       Less drag than CQ-1 but not quite                                                                Less drag than CQ-1 but not                                                    quite                             CQ-4                                                                               1-hexanol  0.018 157 C as low as CQ-2    as little drag as CQ-2                Carbitol                                                                   CQ-5                                                                               Acetate    0.065 217.4 C                                                                              ˜ CQ-4      ˜CQ-4                           Diacetone                                                                  CQ-6                                                                               Alcohol    0.092 169 C ˜ CQ-4      ˜ CQ-4                                                 Slightly less drag than CQ-4,                                                                    Slightly less drag than                                                        CQ-4,                             CQ-7                                                                               1,3-butanediol                                                                            0.031 204 C but not quite as low drag as                                                                     almost but not quite as low                                                    drag as                                                                        CQ-2                                  Ethylene glycol        Definitely more drag than CQ-4.                                                                  More drag than CQ-4 and                                                        slightly                          CQ-8                                                                               di-acetate 0.123 190 C Slightly less drag than CQ-1                                                                     less than CQ-1                        Cellosolve                                                                 CQ-9                                                                               Solvent    0.293 135.6 C                                                                              ˜ CQ-8      ˜ CQ-8                      CQ-10                                                                              1,4-butanediol                                                                            0.036 230 C ˜ CQ-7      ˜ CQ-7                      CQ-11                                                                              1,5-pentanediol                                                                           0.032 240 C ˜ CQ-7      ˜ CQ-7                      __________________________________________________________________________      .sup.(h) Carbowax polyethylene glycol, 6000-7500 molecular weight, Mfg. b      Union Carbide Corp., New York, N.Y. Amount shown includes PEG6000 +            H.sub.2 O 1:1 by weight                                                        OTHER NOTES  See Table I                                                 

Table VIII shows additional high boiling point additives used with a formulation somewhat similar to that used in Table IV, except that in Table VIII the high boiling point additive is used to replace the 1-propanol. Sample JB-22 in Table VIII covers the use of the 1-propanol for comparison purposes and shows that this particular formulation still provides slightly less drag than with any of the other higher boiling point additives tried in its place. As can be seen from the table, however, a number of other organic additives did provide considerable improvement in the overall drag characteristics.

                                      TABLE VIII                                   __________________________________________________________________________     HIGH BOILING POINT ORGANIC ADDITIVES                                           FOR IMPROVING LUBRICITY IN FORMULATION                                         WHEN ALSO USED WITH ISOPROPANOL                                                                                BASIC FORMULATION:                                                                           90.85g                                                                               H.sub.2 O                                                                --    Alcohol-see below                                                        0.104g                                                                               NH.sub.4 OH.sup.(p)                                                      0.10g K.sub.4 B.sub.2                                                                O.sub.7 . 4H.sub.2 O                                                     0.10g NH.sub.4 HCO                                                             --    Organic Additive                                                               see below                                                                0.018g                                                                               Surfactant                                                                     BA-77.sup.(b)                                                            0.20g MPEG-5K.sup.(f)                                            TEST SURFACE: 24" × 18"                                                                      Plate Glass                     Alcohol and Organic                                                                       Amount                                                                              Boiling Point                                             #    Additives  (grams)                                                                             of Additives                                                                          Lubricity                                          __________________________________________________________________________     JB-1 Isopropanol                                                                               6.10 82.3C                                                          Isopropanol                                                                               2.35 82.3C  Considerably less drag nearly dry than JB-1,                                   Also a little less drag                            JB-2 1-propanol 4.05 97.2C  when dry than JB-1 with noticeably better                                      transition wet to completely dry                        Isopropanol                                                                               6.10 82.3C                                                     JB-6 1,3-propanediol                                                                           0.121                                                                               210 C  ˜ JB-2                                            Isopropanol                                                                               6.10 82.3C                                                     JB-7 Carbitol Acetate                                                                          0.076                                                                               217.4C ˜ JB-2                                            Isopropanol                                                                               6.10 82.3C                                                     JB-8 Diethylene glycol      ˜ JB-2                                            di-methyl ether                                                                           0.189                                                                               160 C                                                          Isopropanol                                                                               6.10 82.3C                                                     JB-9 3-Methoxy,1-butanol                                                                       0.185                                                                               161 C  ˜ JB-2                                            Isopropanol                                                                               6.10 82.3C  A little less drag nearly dry than JB-2, Also                                  slightly smoother when                             JB-14                                                                               2,3-butanediol                                                                            0.104                                                                               187 C  completely dry than JB-2                                Isopropanol                                                                               6.10 82.3C                                                     JB-11                                                                               2-Methoxy,1-ethanol                                                                       0.228                                                                               124 C  ˜ JB-2                                            Isopropanol                                                                               6.10 82.3C                                                     JB-17                                                                               Methoxy propanol                                                                          0.180                                                                               120 C  ˜ JB-2                                            Isopropanol                                                                               6.10 82.3C  Very slightly less drag nearly dry than JB-2.                                  Not quite as low drag                              JB-13                                                                               Butyl cellosolve                                                                          0.070                                                                               171.2C nearly dry as JB-14. ˜ JB-14 completely                                  dry.                                                    Isopropanol                                                                               6.10 82.3C  Slightly less drag nearly dry than JB-14.                                      ˜ JB-2 completely                            JB-22                                                                               1-propanol 0.160                                                                               97.2C  dry.                                               __________________________________________________________________________      NOTES  See Table I                                                       

Table IX shows still additional samples where the organic lubricant additives have been selected from what can be categorized as high, intermediate and low boiling point ranges. An examination of the formulations LC-2 and LC-1 in this table, shows that variation in the particular polyethylene glycol and/or methoxypolyethylene glycol compound employed, also can have an effect on the overall lubricity of the cleaning solution. In all cases in Table IX, as well as in preceding Tables VII and VIII the specific formulations shown have been optimized for minimum drag characteristics by adjusting the amounts of one or more of the lubricant additives.

                                      TABLE IX                                     __________________________________________________________________________     ADDITIONAL HIGH BOILING POINT ORGANIC                                          ADDITIVES COMBINED WITH ALCOHOL                                                                     BASIC FORMULATION:                                                                           90.85g H.sub.2 O                                                                -- Alcohol-see below                                                          0.156g NH.sub.4 OH.sup.(o)                                                      -- Organic additive                                                           0.012g Surfactant BX-78.sup.(c)                                                 -- MPEG or PEG - see below                                      TEST SURFACE: 24" × 18" Plate Glass                    Alcohol and                                                                             Amount                                                                              PEG or Amount                                                 #  Organic Additives                                                                       (grams)                                                                             MPEG   (grams)                                                                             Lubricity                                         __________________________________________________________________________        Isopropanol                                                                             6.1                                                                LC-1                                                                              1-propanol                                                                              0.160                                                                               MPEG-5K.sup.(f)                                                                       0.20 Slightly more drag nearly dry than LC-2 but          2,3-butanediol                                                                          0.026            ˜ LC-2 when dry                                Isopropanol                                                                             6.1                                                                LC-2                                                                              1-propanol                                                                              0.160                                                                               PEGC-2OM.sup.(i)                                                                      0.26 Excellent - Very low drag, wet to dry stage          2,3-butanediol                                                                          0.039                                                                 Isopropanol                                                                             6.1                                                                LC-3                                                                              1-propanol                                                                              0.160                                                                               MPEG-5K.sup.(f)                                                                       0.20 Very slightly more drag nearly dry than                                        LC-1                                                 1,3-butanediol                                                                          0.31             ˜ LC-1 and LC-2 when dry                       Isopropanol                                                                             6.1                                                                LC-4                                                                              Methoxy propanol                                                                        0.144                                                                               MPEG-5K.sup.(f)                                                                       0.20 ˜ LC-3                                         2,3-butanediol                                                                          0.026                                                              __________________________________________________________________________      NOTES  See Table I                                                       

In this application, lubricity comparisons have been made by repetitive cleaning of a plate glass or mirror surface, 24" X 18", with the particular formulation being evaluated. A comparison is made with another formulation while noting the differences in friction or drag while wiping with absorbent toweling from the wet, through the intermediate drying stages, to the completely dry condition.

To aid in this admittedly very subjective and relative measurement technique, it was found that more critical frictional differences could be determined by lifting the glass plate from the bench surface and placing it on two narrow wooden strips (one at each end). This technique provided a means for adjustment of the friction between the glass plate and the bench so that the glass would just start to move during the circular wiping motions. The difference in the amount of movement noted between formulations was found to provide a very sensitive indication of lubricity differences.

Unless otherwise stated in a particular test configuration, the cleaning liquid was applied in a measured amount (normally about 1.5 g) from an eyedropper to the center of the glass plate. The liquid was then spread out to a diameter of about 8-10 inches with the finger tips, before starting the wiping operation with a single dry paper towel. Little difference could be found between this mode of application and applying by means of a fine spray from an atomizer type container. It was felt that the eyedropper method would provide a more accurate control of the amount of liquid applied for these comparison tests.

In an attempt to make the relative lubricity measurements more meaningful, comparison was also made with commercially available window cleaners presently available on the market. The cleaners selected were WINDEX, GLASS PLUS, AJAX and EASY-OFF. These were initially compared with each other in the manner just described. In general, it was found that WINDEX provided equivalent, or in some cases superior lubricity throughout the entire wiping transition from the wet to the completely dry stage, to any of the others listed. WINDEX was therefore arbitrarily selected as the commercially available standard with which formulations of the present invention have been compared from a lubricity standpoint.

Table X includes some of the optimized formulations from Tables III, IV, VII, VIII and IX, that have been compared directly with WINDEX. Notations are made for the wet, nearly dry and dry stages during the wiping operation with the absorbent toweling. This table shows that comparatively excellent lubricity (low drag) can be achieved with polyethylene glycol and/or methoxypolyethylene glycol containing window and glass cleaning solutions of this invention.

                                      TABLE X                                      __________________________________________________________________________     LUBRICITY COMPARISONS BETWEEN SELECTED                                         FORMULATIONS AND A COMMERCIALLY AVAILABLE                                      WINDOW AND GLASS CLEANING PRODUCT                                                                                TEST SURFACE:                                                                            24" × 18" Plate Glass        For Formulation                                                                               Lubricity                                                       #     See Table:                                                                              Wet Stage                                                                            Nearly Dry Stage                                                                               Dry Stage                                 __________________________________________________________________________           Commercial                                                               WINDEX                                                                               Product  ˜ JB-22                                                                        Noticeably more drag than CJ-1                                                                 Noticeably more drag than CJ-1            CJ-1  Table III                                                                               ˜ JB-22                                                                        Noticeably more drag than JB-22                                                                More drag than JB-22                                           Less drag than CJ-1                                                                            ˜ JB-22                             CJ-4  Table III                                                                               ˜ JB-22                                                                        More drag than JB-22                                                           Excellent - very low drag wet                                                                  Excellent - very low drag wet to                                               dry                                       JB-22 Table IV ˜ JB-22                                                                        to dry stage    stage                                                          Less drag than CJ-1 but a little                                                               Slightly less drag than CJ-1 but                                               not                                       CQ-2  TABLE VII                                                                               ˜ JB-22                                                                        more than CJ-4  quite as little drag as JB-22                                  Not quite as low drag as JB-22                                                                 ˜CJ-1 More drag than JB-22          JB-14 Table VIII                                                                              ˜JB-22                                                                         but a little less drag than CJ-4                                                               ˜ JB-22, but overall not quite                                           as                                                                             as smooth transition nearly dry           LC-2  Table IX ˜ JB-22                                                                        ˜ JB-22   to completely dry                         __________________________________________________________________________

Ammonium hydroxide has been used as an additive in most prior art liquid window and glass cleaners. It has also been found to be extremely useful with the present invention. It forms an ammonia soap, saponifying oils and fast and is classed as a detergent.

The major advantage of the use of ammonium hydroxide in a liquid cleaner over that of other oil and grease cutters such as the phosphates, borates, etc., is that complete evaporation occurs by the time the surface has been wiped dry and no residue is left behind.

It has been found that ammonium hydroxide can be added to most polyethylene glycol and/or methoxypolyethylene glycol containing formulations in large amounts without any apparent deleterious effect on the cleaning action. As a practical matter, the ammonia content should be limited to an amount that can be reasonably and safely tolerated by the user. For window and glass cleaner applications for household use, the pH of the final solution has, in the preferred formulations for such use, been limited to no more than 10 and preferably to a value closer to 9.5.

In addition to the use of ammonium hydroxide, a large number of other additives to assist in oil and grease film cutting have been evaluated.

Some of these such as sodium oleate, sodium lauryl sulfate, and sodium caseinate were not found to be suitable due to severe glass streaking problems when included in the cleaning solution formulations. Others, such as sodium and potassium hydroxide were not considered because of the potential danger of etching the glass, over long period of time, due to residual amounts of the hydroxide being left on the surface.

However, a number of other grease cutting additives have been evaluated and found to provide a degree of effectiveness in respect to oil and grease film removal from glass and other smooth surfaces. These include one or more of the borates, carbonates, silicates, citrates, phosphates, gluconates, glycolates, etc. which may also be used with added amounts of ammonium hydroxide.

Table XI shows a number of examples where different grease-cutting additives have been used with a basic cleaner formulation. The lubricity comparisons were made as previously explained.

                                      TABLE XI                                     __________________________________________________________________________     EFFECT OF VARIOUS GREASE CUTTING ADDITIVES ON                                  LUBRICITY, RESIDUAL CONTAMINATION AND OIL                                      REMOVAL PROPERTIES                                                                                              BASIC FORMULATION:                                                                           90.8g H.sub.2 O                                                                2.35g Isopropanol                                                              4.05g 1-propanol                                                               0.364g NH.sub.4 OH.sup.(o)                                                     0.011g Surfactant                                                              BA-77.sup.(b)                                                                  0.20g MPEG-5K.sup.(f)                                            TEST SURFACE: 24" × 18" lubricity                                                      test: Plate                                                                    Glass; other tests single                                                      strength mirror                                                     Residual Contamination                          Oil and Grease                                                                             Amount             Test          Oil Removal Test             #    Cutting Additive                                                                           (grams)                                                                              Lubricity -  (Clean Glass) (1 Drop WESSON               __________________________________________________________________________                                                       Oil)                         IK-8 None        --                 None          Very clean                                          Definitely more drag                                                                        None when first applied but                                       both nearly dry and dry                                                                     gets cloudy in certain areas               IK-23                                                                               Na.sub.3 C.sub.6 H.sub.5 O.sub.7 . 2H.sub.2 O                                              0.1   than IK-8    when breathed on                                                                             Clean                        IK-24                                                                               (NH.sub.4).sub.2 HC.sub.6 H.sub.5 O.sub.7                                                  0.1   ˜ IK-23                                                                               ˜ IK-23 Clean                        IK-25                                                                               K.sub.3 C.sub.6 H.sub.5 O.sub.7 . H.sub.2 O                                                0.1   ˜ IK-23                                                                               ˜ IK-23 Clean                             Gluconic Acid.sup.(k)                                                     IK-26                                                                               (50%)       0.143 ˜ IK-8 None          Very Clean                                          A little more drag than                                                        IK-8 both nearly dry and                                IK-27                                                                               KBO.sub.2 . × H.sub.2 O                                                              0.1   dry          None          Extremely Clean              IK-28                                                                               K.sub.3 PO.sub.4 . × H.sub.2 O                                                       0.1   ˜ IK-27                                                                               None          Very Clean                                                       None 1st application but                                          A little more drag nearly                                                                   builds up a film with re-                  IK-29                                                                               K.sub.4 P.sub.2 O.sub.7                                                                    0.1   dry than IK-28                                                                              peated application                                                                           Very clean                   IK-30                                                                               K.sub.5 P.sub.3 O.sub.10                                                                   0.1   ˜ IK-29                                                                               ˜ IK-29 Clean                        IK-31                                                                               (NaPO.sub.3).sub.6                                                                         0.1   ˜ IK-29                                                                               ˜ IK-29 A few oil streaks                 Glycolic Acid.sup.(k)                                                     IK-32                                                                               (70% Min.)  0.132 ˜ IK-23                                                                               ˜ IK-23 Clean                        IK-33                                                                               K.sub.2 B.sub.4 O.sub.7 . 4H.sub.2 O                                                       0.1   ˜ IK-27                                                                               None          Extremely clean ˜                                                        IK-27                        FB-4 NaBO.sub.3 . 4H.sub.2 O                                                                    0.1   ˜ IK-29                                                                               None          Very clean                   FA-13                                                                               NaSiO.sub.3 . 9H.sub.2 O                                                                   0.1   ˜ IK-29                                                                               None          Very clean                   FB-11                                                                               Na.sub.2 CO.sub.3 . 10H.sub.2 O                                                            0.1   ˜ IK-29                                                                               None          Very clean                   __________________________________________________________________________      .sup.(k) NH.sub.4 OH content doubled in order to have sufficient excess t      react with the acid so as to form the appropriate ammonium compound            OTHER NOTES  See Table I                                                 

The "oil removal test" in Table XI, and in subsequent tables of this application unless otherwise specified, consists of placing one drop (˜1.5 g) of oil (in this instance a vegetable oil sold as WESSON oil) in the center of the glass plate test surface. The oil is then rubbed onto the center area of the plate to a diameter of about 8" with the heel of the hand. Next, a measured amount of the specified cleaning formulation is applied to the center of the glass plate with an eyedropper (normally being about 1.5 g of liquid) and is then mixed into the oil film, to at least partially emulsify the mixture, with the tips of the fingers.

The mixture is then wiped from the glass surface with a single paper towel. The emulsified liquid is spread over the entire surface of the glass plate by means of the paper towel at the start of the wiping operation.

When the surface has been wiped completely dry, examination for oil streaks and residue is made under a 500 watt type EAL photoflood lamp or in bright sunlight (no clouds). In either case, the light is reflected onto the glass surface being examined but is not allowed to get behind the observer. In this way, the best possible observation of contaminating films and streaks on the glass has been found to be possible.

As will be explained in more detail later, the "oil removal test", included in Table XI and other tables in this application, is in actuality very severe. It is used to make sure that the inherent oil removal properties of the liquid cleaner solutions of this invention, due to the inclusion of the polyethylene glycol or methoxypolyethylene glycol additive, has not been adversely affected by the incorporation of other additives.

The "residual streaking test" on the clean glass surface is made in the same manner as just explained for the oil removal test except that no oil is used. That is, the liquid formulation is applied to the center of the clean glass surface in a measured amount (again, normally ˜1.5 g). The liquid is then spread out on the glass to a diameter of about 8-10" with the finger tips, and then wiped dry using a single paper towel. Again, the liquid is spread over the entire surface of the glass plate by means of the paper towel at the start of the wiping operation. Examination is by means of the same lighting method also described earlier.

The "residual streaking test" on an already clean glass surface has been included in Table XI, and other tables in this application, to determine if added solids are being left behind as a visible residue. It is also a way of making sure that the polyethylene glycol and/or methoxypolyethylene glycol additive in these formulations is ultimately applied to the glass surface in a uniform, ultra thin and invisible film.

Two of the formulations in Table XI, #IK-27 and #IK-33, respectively, even with excessive oil present showed excellent oil film removal properties. These were formulations incorporating potassium metaborate and potassium tetraborate, respectively, as the grease cutting additives.

For the nominal amounts of additives used in these various formulations in Table XI, none caused residual streaking on the clean glass (at least for the initial application). It has been found, however, that the majority of the phosphates will cause a cloudy film to build up on the glass surface after several repeated applications, making their use in a practical glass cleaning solution very questionable. The only phosphates that have been found that do not exhibit this property to an objectionable degree are the tribasic sodium and potassium phosphates (Na₃ PO₄ and K₃ PO₄).

The reason for this strange behavior of many of the phosphate additives is not understood, but it is suspected that some combination occurs between the phosphate and the polyethylene glycol and/or methoxypolyethylene glycol present in the solution.

The citrates were found in subsequent tests to do an excellent job of aged oil film removal when used as an additive to formulations of this invention. However, as can be seen in test samples IK-23, IK-24 and IK-25 in Table XI, even when used in the small quantities employed here, their use causes a cloudy residue to appear when the glass is breathed on or is left in a humid atmosphere.

The most disappointing finding while conducting the tests of Table XI was that even with the very small percentages involved, almost every grease cutting additive tried caused a noticeable increase in the drag while wiping the glass surface from the wet to the dry stage with absorbent toweling.

A concerted effort was therefore made to try and find an oil and grease cutting additive that would be effective but hopefully at the same time not degrade the overall lubricity properties of the cleaner when used in amounts sufficient to be effective.

During the course of this evaluation a unique finding was made. Not only was a family of effective inorganic oil and grease cutting additives found, but is was also discovered that these additives were capable of providing even greater lubricity to the polyethylene glycol and/or methoxypolyethylene glycol containing formulations of this invention than had previously been possible through the use of organic lubricants alone. This family of additives constitutes ammonium bicarbonate, ammonium carbonate and mixtures thereof, or mixtures of ammonium carbonate and ammonium carbamate.

Ammonium bicarbonate (NH₄ H CO₃) is a well defined inorganic compound, soluble in water, is non-toxic, has a specific gravity of 1.586 and decomposes in air evolving ammonia and carbon dioxide gas at 36° C. to 60° C. Ammonium carbonate, on the other hand, is defined, depending on the reference source or supplier as (NH₄)₂ CO₃, (NH₄)₂ CO₃ ·2H₂ O or as an unspecified mixture of ammonium carbonate and ammonium carbamate (NH₄ CO₂ NH₂). Ammonium carbamate by itself has been tested and found to slightly degrade lubricative effects in this application. However, the ammonium carbonate stated to be a mixture containing ammonium carbamate gave excellent results from the lubricity standpoint. Ammonium carbonate is unstable in air, decomposing to ammonium bicarbonate.

Both the ammonium bicarbonate and carbonate were found to be stable in water solution to at least 150° F. At 160° F. the ammonium carbonate appears, from pH measurements after the solution was cooled to room temperature, to have converted to the bicarbonate form. Temperatures well below 150° F. would be expected for normal shipping, storage and use conditions. The upper temperature limit for the use of the bicarbonate has not been determined.

The reason for the greatly improved lubricity characteristics obtained by the addition of the ammonium bicarbonate or carbonate is not known. This may be due entirely to a unique crystal structure of these particular ammonia compounds. A more plausible explanation, however, is that during the wiping and drying of the liquid cleaner against the surface being cleaned (by the absorbent toweling) sufficient rubbing action occurs to cause at least partial decomposition of the ammonium compound(s). Whether the decreased friction is due to physical changes in the ammonium carbonate (or bicarbonate) crystal structure during this rubbing operation or the formation of a carbon dioxide-ammonia gas film, or both, is open to question. In any event, it has been found that the addition of these inorganic compounds greatly increases the lubricity of such liquid cleaning solutions during the partially dry to nearly dry and even the completely dry stages.

Table XII shows tests run with varying amounts of ammonium bicarbonate and ammonium carbonate added to an otherwise standard formulation. In this test the ammonium bicarbonate was a "certified" grade and the ammonium carbonate a "purified" grade. Although not included in the table, a "certified" grade of ammonium carbonate consisting of "a mixture of ammonium carbonate and ammonium carbamate of varying proportions" was also tried with equivalent results to the ammonium carbonate. Ammonium carbamate was also used in place of the ammonium bicarbonate or carbonate with this same basic formulation and found to impart a slight reduction in lubricity.

                                      TABLE XII                                    __________________________________________________________________________     EFFECT OF VARYING AMOUNTS OF AMMONIUM BICARBONATE                              AND AMMONIUM CARBONATE ADDITIVES ON LUBRICITY,                                 RESIDUAL CONTAMINATION AND OIL REMOVAL PROPERTIES                                                           BASIC FORMULATION:                                                                           90.85g H.sub.2 O                                                               6.10g Isopropanol                                                              0.16g 1-propanol                                                               0.104g NH.sub.4 OH.sup.(p)                                                      -- Carbonate-see below                                                        0.018g Surfactant                                                              BA-77.sup.(b)                                                                  0.20g MPEG-5K.sup.(f)                                            TEST SURFACE: 24" × 18" Lubricity                                                      Test: Plate                                                                    Glass; other tests single                                                      strength mirror                                  Amount               Residual Contamination                                                                     Oil Residual Test                #  Carbonate Additive                                                                       (grams)                                                                             Lubricity       (Clean Glass)                                                                              (1 Drop WESSON                   __________________________________________________________________________                                                   Oil)                                                                           Clean to Very                    JE-1                                                                              None      --                   None        Clean                                              Slightly more drag nearly                                                      dry than JE-3 and JE-5.                                      JE-2                                                                              NH.sub.4 HCO.sub.3                                                                       0.05 ˜ Same dry                                                                               None        Very Clean                                         Excellent-much less drag than                                                  JE-1 both nearly dry and dry.                                JE-5                                                                              NH.sub.4 HCO.sub.3                                                                       0.075                                                                               Excellent transition wet to dry                                                                None        Very Clean                                         Excellent- ˜ JE-5 Can't tell                           JE-3                                                                              NH.sub.4 HCO.sub.3                                                                       0.10 difference      None        Very Clean                                         A little more drag nearly dry                                                  than JE-3 and JE-5. ˜ same dry.                                          Very slightly more drag than                                 JE-4                                                                              NH.sub.4 HCO.sub.3                                                                       0.15 JE-2 nearly dry but better dry                                                                 None        Very Clean                                         Slightly more drag nearly dry                                                  than JE-9 but ˜ same dry.                                                Definitely less drag than JE-1                               JE-6                                                                              (NH.sub.4).sub.2 CO.sub.3                                                                0.05 both nearly dry and dry                                                                        None        Very Clean                                         Excellent- ˜ JE-5 Can't tell                           JE-9                                                                              (NH.sub.4).sub.2 CO.sub.3                                                                0.075                                                                               difference      None        Very Clean                                         Excellent- ˜ JE-9 Can't tell                           JE-7                                                                              (NH.sub.4).sub.2 CO.sub.3                                                                0.10 difference      None        Very Clean                                         Very slightly more drag than                                                   JE-6 nearly dry. ˜ JE-9 and                            JE-8                                                                              (NH.sub.4).sub.2 CO.sub.3                                                                0.15 JE-7 when dry   None        Very Clean                       __________________________________________________________________________      NOTES  See Table I                                                       

As can be seen in Table XII, the 0.075-0.15 gram range appeared to be optimum for obtaining minimum drag from either the ammonium bicarbonate or ammonium carbonate additives with this basic formulation. No discernible difference between the use of the two compounds could be found as far as this test was concerned. The same proportions of water to ammonium bicarbonate or carbonate content also appear to be optimum with other formulation variations; however, amounts as low as 0.025 grams of carbonate or bicarbonate to as great as 0.3 grams to 92.5 grams of H₂ O or on the order of 3 weight percent have been used without undue drag or residual deposits on the glass.

An additional finding of considerable importance is that a number of other grease cutting additives, that in themselves will cause a noticeable increase in the drag characteristics, can be used without degradation of lubricity when used in combination with one of the ammonium carbonate, ammonium bicarbonate family of compounds. In fact, in many cases, the lubricity can be as good as if the ammonium compound were used alone. Table XIII shows a number of formulations using this type of combination.

                                      TABLE XIII                                   __________________________________________________________________________     EFFECT OF GREASE CUTTING ADDITIVES LUBRICITY                                   AND OTHER PROPERTIES WHEN USED IN COMBINATION                                  WITH AMMONIUM BICARBONATE                                                                                       BASIC FORMULATION:                                                                          90.8g H.sub.2 O                                                                2.35g Isopropanol                                                              4.05g 1-propanol                                                               0.104g NH.sub.4 OH.sup.(o)                                                      -- Grease Cutting                                                             Additive-see below                                                             0.011g Surfactant                                                              BA-77.sup.(b)                                                                  0.27g PEG 20K                                                                  linear.sup.(j)                                                   TEST SURFACE: 24" × 18" Lubricity                                                      Test: Plate                                                                    Glass; other tests single                                                      strength mirror                                   Amount                Residual Contamination                                                                     Oil Removal Test            #    Grease Cutting Additive                                                                    (grams)                                                                             Lubricity        Test (Clean Glass)                                                                         (1 Drop WESSON              __________________________________________________________________________                                                        Oil)                                              Considerably more drag nearly dry                                              than IX-45 and a little more drag                                                               None - Leaves clean                     IX-49                                                                               None        --   completely dry   glass surface                                                                              Clean                                                              None - Leaves very                      IX-45                                                                               NH.sub.4 HCO.sub.3                                                                         0.1  Excellent - Very low drag                                                                       clean glass surface                                                                        Very Clean                                                         None - Leaves                                NH.sub.4 HCO.sub.3                                                                         0.1                   exceptionally clean                                                                        Exceptionally               IX-3 KBO.sub.2 . × H.sub.2 O                                                              0.1  ˜ IX-45    glass surface                                                                              Clean                            NH.sub.4 HCO.sub.3                                                                         0.1                                                           IX-21                                                                               K.sub.2 B.sub.4 O.sub.7 . 4H.sub.2 O                                                       0.1  ˜ IX-45    ˜ IX-3                                                                               ˜ IX-3                                                       Almost none - Slight                                                           cloudy film in a few                         NH.sub.4 HCO.sub.3                areas, especially                            Gluconic Acid.sup.(k)                                                                      0.1                   corners when breathed                   IX-5 (50%)       0.088                                                                               ˜IX-45     on          ˜ IX-45                                     ˜ IX-45 (When using 0.1 g                               NH.sub.4 HCO.sub.3                                                                         0.1  sodium citrate drag is increased                         IX-9 Na.sub.3 C.sub.6 H.sub.5 O.sub.7 . 2H.sub.2 O                                              0.05 over that nearly dry of IX-45)                                                                  ˜ IX-5                                                                               ˜ IX-45                    NH.sub.4 HCO.sub.3                                                                         0.1                                                           IX-2 Na.sub.3 PO.sub.4 . 12H.sub.2 O                                                            0.1  ˜ IX-45    ˜ IX-45                                                                              ˜ IX-45                    NH.sub.4 HCO.sub.3                                                                         0.1  Very slightly more drag nearly                           IX-19                                                                               NaBO.sub.3 . 4H.sub.2 O                                                                    0.1  dry to dry than IX-45                                                                           ˜IX-45                                                                               ˜IX-45                     (NH.sub.4).sub.2 CO.sub.3                                                                  0.1                                                           IX-60                                                                               KBO.sub.2 . × H.sub.2 O                                                              0.1  ˜ IX-3 Can't tell difference                                                              ˜ IX-3                                                                               ˜                     __________________________________________________________________________                                                        IX-3                         .sup.(j) Carbowax polyethylene glycol, 18,000-19,000 molecular weight,         Mfg. by Union Carbide Corporation, New York, N.Y. Amount shown includes        PEG20,000 linear + H.sub.2 O 1:2 by weight                                     OTHER NOTES  See Tables I & XI                                           

As can be seen from the table, the best overall results were obtained from formulations IX-3 and IX-4 containing the potassium metaborate and potassium tetraborate, respectively. Not only was the lubricity excellent but in addition, repeated tests and comparisons showed that the glass surface was left in an exceptionally clean condition, both with clean and oil contaminated glass prior to its use. Also, there is absolutely no indication of any cloudy film when the freshly cleaned surface is breathed on or placed in a humid atmosphere.

An examination of formulations IX-6 and IX-9 in Table XIII shows that while the lubricity is excellent with the ammonium bicarbonate present, the use of the citrate and glycolate in the proportions involved here tend to leave a cloudy film on portions of the glass, (especially in the corners or at the edges where an excess probably can build up) when used in high humidity conditions. The citrate, in particular, because of its observed excellent oil and grease cutting properties when used in such formulations could, however, be considered for uses other than cleaning windows and mirrors where the highest optical clarity may not be important.

In subsequent tests with sodium citrate, potassium citrate, and ammonium citrate, it is interesting to note that only the sodium citrate provided low drag characteristics when used in combination with the ammonium bicarbonate.

A similar situation was found in the use of trisodium phosphate (Na₃ PO₄ ·12H₂ O) as compared to tri-potassium phosphate (K₃ PO₄ ·H₂ O). Again, the sodium compound was found to provide no additional drag when used with ammonium carbonate or ammonium bicarbonate while the tri-potassium phosphate added very considerable drag.

In the case of the borates, the reverse situation, although not as pronounced, exists. That is, the potassium metaborate and potassium tetraborate provided noticeably lower drag characteristics than their sodium counterparts when used with the ammonium carbonate or ammonium bicarbonate lubricant system.

As stated earlier, ammonium hydroxide has often been incorporated in the preferred formulations of this invention. While by no means a necessity, it can assist in the overall oil, grease and other contamination removal from the surface being cleaned without fear of leaving residual deposits.

Table XIV provides an idea of changes in pH that can be expected with varying the amount of ammonium hydroxide (28% NH₃) added to three difference basic formulations: one with no added grease cutters, one with ammonium bicarbonate and potassium tetraborate, and one with ammonium bicarbonate and the more basic potassium metaborate.

                                      TABLE XIV                                    __________________________________________________________________________     EFFECT OF ADDING AMMONIUM HYDROXIDE ON pH                                      OF THREE FORMULATIONS WITH AND WITHOUT                                         GREASE CUTTING ADDITIVES                                                                                           BASIC FORMULATIONS                                                                           85.9g H.sub.2 O                                                                10.00g Isopropanol                                                             0.261g 1-propanol                                                               -- NH.sub.4 OH.sup.(p)                                                        -see below                                                                      -- Grease Cutters-                                                              see below                                                                     -- Organic Lubricant                                                            see below                                                                    0.012g Surfactant                                                              BX-78.sup.(e)                                                                  0.26g PEGC-20M.sup.(i)       #  Additives(s)                                                                          Amount                                                                              pH  #  Additive(s)                                                                              Amount                                                                              pH   #  Additive(s)                                                                            Amount                                                                              pH                   __________________________________________________________________________     J-1                                                                               None   --   ˜5                                                                           JD-1                                                                              None      --   ˜5                                                                            JN-1                                                                              None    --   ˜5             J-2                                                                               2,3-butanediol                                                                        0.039                                                                               ˜5                                                                           JD-2                                                                              NH.sub.4 HCO.sub.3                                                                       0.08 ˜6                                                                            JN-2                                                                              NH.sub.4 HCO.sub.3                                                                     0.08 ˜6                2,3-butanediol                                                                        0.039       NH.sub.4 HCO.sub.3                                                                       0.08         NH.sub.4 HCO.sub.3                                                                     0.08                      J-3            ˜8.5                                                                         JD-3              ˜8.5                                                                          JN-3            ˜9                NH.sub.4 OH                                                                           0.052       K.sub.2 B.sub.4 O.sub.7 . 4H.sub.2 O                                                     0.10         KBO.sub. 2 . × H.sub.2                                                   O       0.10                         2,3-butandediol                                                                       0.039       NH.sub.4 HCO.sub.3                                                                       0.08         NH.sub.4 HCO.sub.3                                                                     0.08                      J-4            ˜9                                                                           JD-4                                                                              K.sub.2 B.sub.4 O.sub.7 . 4H.sub.2 O                                                     0.10 ˜9                                                                            JN-4                                                                              KBO.sub.2 . × H.sub.2                                                    O       0.10 ˜9.5              NH.sub.4 OH                                                                           0.104       NH.sub.4 OH                                                                              0.052        NH.sub.4 OH                                                                            0.052                        2,3-butanediol                                                                        0.039       NH.sub.4 HCO.sub.3                                                                       0.08         NH.sub.4 HCO.sub.3                                                                     0.08                      J-5            ˜9.5                                                                         JD-5                                                                              K.sub.2 B.sub.4 O.sub.7 . 4H.sub.2 O                                                     0.10 ˜9.5                                                                          JN-5                                                                              KBO.sub.2 . × H.sub.2                                                    O       0.10 ˜10               NH.sub.4 OH                                                                           0.156       NH.sub.4 OH                                                                              0.104        NH.sub.4 OH                                                                            0.104                        2,3-butanediol                                                                        0.039       NH.sub.4 HCO.sub.3                                                                       0.08                                           J-6            ˜10                                                                          JD-6                                                                              K.sub.2 B.sub.4 O.sub.7 . × 4H.sub.2 O                                             0.10 ˜10                                    NH.sub.4 OH                                                                           0.208       NH.sub.4 OH                                                                              0.156                                          J-7                                                                               2,3-butanediol                                                                        0.039                                                                               ˜10.2                                                        NH.sub.4 OH                                                                           0.260                                                                J-9                                                                               2,3-butanediol                                                                        0.039                                                                               ˜10.5                                                        NH.sub.4 OH                                                                           0.364                                                                __________________________________________________________________________      NOTES  See Table I                                                       

Table XV shows some tests made with a variety of grease and oil cutting additives to determine their relative ability to cut aged vegetable oil and aged animal fat films on a flat mirror surface. The vegetable oil (WESSON oil) and animal fat (bacon grease) was carefully spread as a uniform but thin film over the surface of several 24"×18" test mirrors and allowed to age for a little over three days. The test was conducted by simply applying a given amount of the cleaning solution to approximately one-half of the mirror surface, and then rubbing and wiping the surface with a paper towel until dry. The surface was then lightly washed with a wet sponge with clean tap water. This removed any well emulsified oil and fat and any residual cleaner that might have remained on the surface. The areas of glass still having oil and fat film attached could be easily seen at this point because of the water film separation.

                                      TABLE XV                                     __________________________________________________________________________     EFFECT OF OIL & GREASE CUTTING                                                 ADDITIVES ON REMOVAL OF AGED                                                   OIL AND GREASE FILMS                                                                                      BASIC FORMULATION:                                                                           90.8g H.sub.2 O                                                                2.3g Isopropanol                                                               4.05g 1-propanol                                                               0.104g NH.sub.4 OH.sup.(p)                                                      -- Grease Cutting Aid                                           see below                                                                                    0.011g Surfactant BA-77.sup.(b)                                                0.27g PEG-20,000 linear                                          TEST SURFACE: 24" × 18" Single Strength                                                Mirror                                       Oil and Grease Cutting                                                                     Amount Aged Vegetable Oil and Animal Fat Film Removal                                 Tests.sup.(1)                                        #      Additives   (grams)                                                                               (Results were essentially the same for both                                    types of film)                                       __________________________________________________________________________     IX-49  None        --                                                          IX-45  NH.sub.4 HCO.sub.3                                                                         0.1    A little better film removal than IX-49 but not                                as good as IX-3                                      IX-7   NH.sub.4 HCO.sub.3                                                                         0.1                                                                Na.sub.3 C.sub.6 H.sub.5 O.sub.7 . 2H.sub.2 O                                              0.1    Best film removal properties in test                 IX-7A  NH.sub.4 HCO.sub.3                                                                         0.1                                                                Na.sub.3 C.sub.6 H.sub.5 O.sub.7 . 2H.sub.2 O                                              0.05   Not quite as good film removal as IX-7               IX-5   NH.sub.4 HCO.sub.3                                                                         0.1    Not quite as good film removal as IX-3,                                        probably just slightly better than                          Glycolic Acid.sup.(k)                                                                      0.09   IX-45 but hard to tell                               IX-3   NH.sub.4 HCO.sub.3                                                                         0.1                                                                KBO.sub.2 . × H.sub.2 O                                                              0.1    Not quite as good film removal as IX-7A and                                    IX-2                                                 IX-2   NH.sub.4 HCO.sub.3                                                                         0.1                                                                Na.sub.3 PO.sub.4 . 12H.sub.2 O                                                            0.1    ˜IX-7A                                         WINDEX Commercial Product                                                                         --     ˜IX-7A and IX-2                                __________________________________________________________________________      .sup.(1) Vegetable oil film was WESSON Oil. Animal fat film was bacon          grease. Both films applied to flat mirror surface as thin films and aged       days before starting test                                                      OTHER NOTES  See Tables I, XI & XIII                                     

It should be stated that the comparisons in Table XV are necessarily relative and also somewhat crude in nature. The principal conclusions that may be made is that, for the amounts of grease cutting additives present, the sodium citrate containing formulation, IX-7, did the best film removal job and the tri-sodium phosphate, IX-2, the next best with the potassium metaborate, IX-3, a close third.

As well as being a most effective lubricating aid, results of formulation IX-45 in the table shows that the ammonium bicarbonate is also acting as an oil and grease cutting additive.

WINDEX, a commercially available window and glass cleaner was also included in this test and gave film cutting results that were roughly equivalent to the tri-sodium phosphate of formulation IX-2. Each test in Table XV was repeated at least twice using a new, contaminated mirror surface.

An important finding is that the ammonium bicarbonate or carbonate is not dependent on the presence of polyethylene glycol and/or methoxypolyethylene glycol in the solution for the achievement of its unique lubricating properties.

It has been found, for example, that the ammonium carbonate or ammonium bicarbonate can be added in small amounts to a variety of window, glass and chrome cleaners presently on the market and show a significant increase in the overall lubricity of such products.

Table XVI shows comparisons of several such household type window cleaners purchased on the market. Ammonium bicarbonate as a lubricant has been added to one sample of each type of cleaner listed in the table but not to the other. Also included is another one of the formulations of my invention, for comparison purposes.

It will be noted that, in every instance, the addition of the ammonium bicarbonate has dramatically decreased the drag properties found for any given type of cleaner while it is being wiped from the wet to the dry stage with a paper towel.

                                      TABLE XVI                                    __________________________________________________________________________     COMPARISONS OF FORMULATION EB-2 AND                                            COMMERCIAL WINDOW AND GLASS CLEANERS                                           WITH AND WITHOUT AMMONIUM BICARBONATE                                          ADDED AS INORGANIC LUBRICANT                                                                          BASIC FORMULATION                                                                            92.5g H.sub.2 O                                                  For # EB-2 Only:                                                                             2.40g Isopropanol                                                              3.160g 1-propanol                                                              0.36g NH.sub.4 OH.sup.(o)                                                      0.016g Surfactant BA-77.sup.(b)                                                0.16g MPEG-5K.sup.(f)                                            TEST SURFACE: 24" × 18" Lubricity Test:                                                Plate                                                                          Glass; other tests single                                                      strength mirror                                      Amount                          Oil Removal Test                    #  Formulation                                                                            (grams)                                                                             Lubricity                  (1 Drop WESSON                      __________________________________________________________________________                                                Oil)                                0  #EB-2   100  Considerably more drag nearly dry and a little                                                            Clean                                  (see above)  drag completley dry than #1. Also a little less                                drag than #2 both nearly dry and dry                           1  #EB-2   100  Excellent - Low drag nearly dry and dry. Very                                                             Very Clean                             NH.sub.4 HCO.sub.3                                                                     0.10 transition wet to completely dry                               2  WINDEX  100  Much more drag than #1, especially noticeable                                                             A great many oil                                    nearly dry                 streaks all over                                                               surface                                                                        A great many oil                    3  WINDEX  100  ˜ #1 nearly dry. Much less drag than #2 nearly                                                      streaks all over                       NH.sub.4 HCO.sub.3                                                                     0.10 and noticeably smoother when completely                                                                   surface                                             ˜ #2 but probably very slightly more drag when                           nearly                     A great many oil                                    dry                        streaks all over                    4  GLASS PLUS                                                                             100                             surface                                                                        A great many                        5  GLASS PLUS                                                                             100  ˜3 Hard to tell any difference but probably                                                         oil streaks                            NH.sub.4 HCO.sub.3                                                                     0.10 slightly more drag when completely dry                                                                    all over surface                                                               A great many                                                                   oil streaks                         6  AJAX    100  ˜ 2 Hard to tell any difference                                                                     all over surface                                                               A great many                        7  AJAX    100                             oil streaks all                        NH.sub.4 HCO.sub.3                                                                     0.10 ˜3 Hard to tell any difference                                                                      over surface                                                                   A great many                                        Definitely more drag than #2 including more drag                                                          oil streaks all                     8  EASY OFF                                                                               100  nearly dry and completely dry                                                                             over surface                                                                   A great many                        9  EASY OFF                                                                               100  Much less drag wet to nearly dry than #8 but                                                              oil streaks all                        NH.sub.4 HCO.sub.3                                                                     0.10 considerable drag completely dry                                                                          over surface                        __________________________________________________________________________      NOTES  See Table I                                                       

Table XVIA shows the use of both ammonium bicarbonate and ammonium carbonate in varying amounts added to WINDEX. The results show that maximum lubricity is obtained with 0.1 grams per 98.2 grams of WINDEX for both types of carbonate additives although a range from about 0.05 grams to about 0.3 grams have been used with success. Essentially no difference from a lubricity standpoint could be determined between the use of ammonium bicarbonate or the ammonium carbonate.

Surface active agents (or surfactants) have been found to be useful additives to the liquid cleaning solutions of this invention. Only certain surfactants have been found to be helpful, however, and these have all been from a group that are primarily classed as wetting agents and penetrating agents. Their main function in this application is to enhance wicking of the cleaning solution into the absorbent toweling used to wipe and dry the surface being cleaned. They also help the spreading of the solution over the surface to which the solution is being applied.

                                      TABLE XVI A                                  __________________________________________________________________________     EFFECT OF VARYING AMOUNTS OF AMMONIUM BICARBONATE                              AND AMMONIUM CARBONATE ON LUBRICITY OF WINDEX, A                               COMMERCIAL WINDOW AND CLASS CLEANER                                                            BASIC FORMULATION:                                                                              98.2g WINDEX                                                                   --Carbonate Additive                                                           see below                                                                      24" × 8" Lubricity Test: Plate                                           Glass; other tests single                                     TEST SURFACE:    strength mirror                                                                          Residual                                        Amount                         Contamination Test                  #   Additive                                                                               (grams)                                                                            Lubricity                  (Clean Class)                       __________________________________________________________________________     LE-1                                                                               None        A lot more drag nearly dry than LE-4, also                                                                Extremely Clean                                     more drag when dry                                             LE-1.5                                                                             NH.sub.4 HCO.sub.3                                                                     0.025                                                                              A little less drag than LE-1, but more drag                                                               Extremely Clean                                     LE-2, both nearly dry and when dry                             LE-2                                                                               NH.sub.4 HCO.sub.3                                                                     0.05                                                                               Noticeably less drag nearly dry and completely dry                                                        Extremely Clean                                     LE-1.                                                                          A little more drag nearly dry and dry than LE-4                LE-3                                                                               NH.sub.4 HCO.sub.3                                                                     0.075                                                                              Very slightly more drag nearly dry than LE-4 but                                                          Extremely Clean                                     same dry                                                       LE-4                                                                               NH.sub.4 HCO.sub.3                                                                     0.10                                                                               Very low drag - good transition wet to dry                                                                Extremely Clean                     LE-5                                                                               NH.sub.4 HCO.sub.3                                                                     0.125                                                                              ˜ LE-3               Extremely Clean                     LE-6                                                                               NH.sub.4 HCO.sub.3                                                                     0.15                                                                               ˜ LE-2 Both nearly dry and dry                                                                      Extremely Clean                     LE-6.5                                                                             NH.sub.4 HCO.sub.3                                                                     0.3 ˜ LE-1.5 Nearly dry, not quite as smooth as                                                         Extremely Clean                                     appears to have slight residue on surface of glass                             when first reaching dry stage                                  LE-7                                                                               NH.sub.4 HCO.sub.3                                                                     0.1 ˜ LE-4 (and LE-9) Can't tell any difference                                                         Extremely Clean                         KBO.sub.2 . × H.sub.2 O                                                          0.1                                                                LE-8                                                                               (NH.sub.4).sub.2 CO.sub.3                                                              0.05                                                                               ˜ LE-2               Extremely Clean                     LE-9                                                                               (NH.sub.4).sub.2 CO.sub.3                                                              0.1 ˜ LE-4               Extremely Clean                     LE-10                                                                              (NH.sub.4).sub.2 CO.sub.3                                                              0.15                                                                               ˜ LE-6               Extremely Clean                     __________________________________________________________________________

It is of primary importance that the surfactant used is not so powerful in its detersive and emulsifying properties as to cause a combination or mixing to any noticeable degree of the oil and grease contamination with the polyethylene or methoxypolyethylene glycol constituent of the cleaning solution. Should such a combination occur, the inherent oil and grease repelling action of the polyethylene and/or methoxypolyethylene glycol additive will be reduced or lost.

The surfactant selected for use in these liquid cleaning solutions should also leave no noticeable residue nor cause fogging, an undue increase in drag while wiping the surface dry, nor introduce other undesirable side effects.

Table XVII contains a list of several surfactants, classed as wetting and penetrating agents, that have been found suitable for use in these polyethylene glycol and/or methoxypolyethylene glycol containing solutions. Also indicated in the table is the general chemical description, manufacturer's name and major industrial uses. In addition, Table XVII shows the generally preferred amounts that can be used for each of these particular surfactants for window and glass cleaning applications.

                                      TABLE XVII                                   __________________________________________________________________________     PARTIAL LIST OF SUITABLE SYNTHETIC SURFACTANTS FOR USE WITH                    POLYETHYLENE OR METHOXYPOLYETHYLENE GLYCOL CONTAINING LIQUID                   CLEANING SOLUTIONS                                                                                                             *Generally Preferred           Surfactant                                                                             Chemical                                Amounts (Referred to                                                           H.sub.2 O                      Designation                                                                            Description                                                                              Manufacturer                                                                               Other Uses        by weight)                     __________________________________________________________________________     NEKAL   sodium    GAF Corporation                                                                            wetting dispensing penetrating                                                                   .008-.04%                      BA-77   alkylnaphthelene                                                                         New York, New York                                                                         and anti-static agent in paper                           sulfonate             and textile industry. Wetting                                                  of powdered insecticides                         NEKAL   sodium    GAF Corporation                                                                            wetting dispensing penetrating                                                                   .005-.03%                      BX-78   alkylnaphthelene                                                                         New York, New York                                                                         and anit-static agent in paper                           sulfonate             and textile industry. Wetting                                                  of powdered insecticides                         NEKAL   sulfonated                                                                               GAF Corporation                                                                            wetting, re-wetting and pene-                                                                    .001-.008%                     WT-27   aliphatic New York, New York                                                                         trating agent for paper and                              polyester             dyeing and glass cleaning                        ANTAROX modified linear                                                                          GAF Corporation                                                                            textile wetting, metal cleaning                                                                  .004-.027%                     BL-225  aliphatic New York, New York                                                                         rinse aid in commercial                                  polyester             washing                                          FLUORAD potassium 3-M Company wetting, pentrating and form-                                                                    .001-.008%                     FC-95   per-      St. Paul, Minnesota                                                                        ing agents suitable for highly                           fluoroalkyl           basic and acidic solutions in                            sulfonate             plating and anodizing                            FLUORAD potassium 3-M Company wetting, penetrating and foam-                                                                   .0015-.01%                     FC-98   per-      St. Paul, Minnesota                                                                        ing agents suitable for highly                           fluoroalkyl           basic and acidic solutions in                            sulfonate             plating and anodizing                            __________________________________________________________________________      *NOTE:                                                                         This amount has generally been found to be enough to improve wicking into      absorbent toweling but small enough to avoid streaking or eventual             clouding of window and mirror surfaces.                                  

The list of surfactants in Table XVII is only intended to show a few specific choices that have been found to provide, by actual experimentation, satisfactory results. There are, of course, many others that will undoubtedly perform just as well, that can be selected from among the extremely large number of surfactant products now available on the market.

It should be pointed out that the use of a synthetic surfactant in these polyethylene and/or methoxypolyethylene glycol containing liquid cleaning solutions is by no means essential. The alcohol, for example, is in itself an excellent wetting and penetrating agent and appears to have no adverse affect on the oil and grease repelling properties of the polyethylene and/or methoxypolyethylene glycol component. With careful selection of type and amount, however, a surfactant as described above, and in Table XVII, can reduce the quantity of alcohol required for a given wicking rate and also appears in some instances to slightly accelerate transfer of oil and grease contamination into the toweling.

A wide molecular weight range of polyethylene and methoxypolyethylene glycols have been evaluated and found to be usable as the oil and grease repelling additive of the invention.

Table XVIII covers comparative tests made using a basic liquid cleaner formulation with polyethylene glycols ranging in molecular weight from about 400 to 20,000. Table XIX covers similar tests using methoxypolyethylene glycols with molecular weights ranging from 500 to 5,000. Table XX shows specific chemical and physical properties of the polyethylene and methoxypolyethylene glycol compounds used in all preceding tables including Tables XVIII and XIX. All of the compounds listed in Table XX are manufactured by Union Carbide Corporation, New York, N.Y., and are sold under the product name of CARBOWAX.

                                      TABLE XVIII                                  __________________________________________________________________________     PROPERTY VARIATIONS DUE TO USING OPTIMUM                                       AMOUNTS OF POLYETHYLENE GLYCOL ADDITIVES                                       OF DIFFERENT MOLECULAR WEIGHTS                                                                       BASIC FORMULATION:                                                                            90.8g H.sub.2 O                                                                2.35g Isopropanol                                                              4.05g 1-propanol                                                               0.364g NH.sub.4 OH.sup.(o)                                                     0.011g Surfactant BA-77.sup.(b)                                                24" × 18" Lubricity Test:                                                Plate                                                           TEST SURFACE:  Glass; other test single                                                       strength mirror                                           Molecular                 Residual                                 Polyethylene                                                                          Amount                                                                              Weight                    Contamination                                                                           Oil Removal Test            #   Glycol (grams)                                                                             Range Lubricity           (Clean Glass)                                                                           (1 Drop Wesson              __________________________________________________________________________                                                        Oil)                        CW-15                                                                              PEG-400.sup.(m)                                                                       0.10 380-420                                                                              Definitely more drag nearly dry                                                                    None     Clean Surface                                     and completely dry than CW-8,                                                  CW-3, CW-1 and CW-19. Chatters with                                            back and forth motion of paper                                                 towel when surface becomes dry                           CW-8                                                                               PEG-1540.sup.(g)                                                                      0.20 1300-1600                                                                            A little more drag nearly dry and                                                                  None     Clean Surface                                     completely dry than CW-3                                 CW-3                                                                               PEG-4000.sup.(e)                                                                      0.18 3000-3700                                                                            Very slightly more drag nearly dry                                                                 None     Clean Surface                                     and completely dry than CW-1, but                                              nearly the same                                          CW-1                                                                               PEG-6000.sup.(h)                                                                      0.20 6000-7500                                                                            Excellent- Low drag and smooth                                                                     None     Clean Surface                                     transition wet to dry stages                                             18,000-                                                                              ˜CW-1 Can't tell any difference                    CW-19                                                                              PEGC-20M.sup.(i)                                                                      0.26 19,000                                                                               with this particular formulation                                                                   None     Clean                       __________________________________________________________________________                                                        Surface                      .sup.(e) Carbowax polyethylene glycol, 3000-3700 molecular weight, Mfg. b      Union Carbide Corporation, New York, N.Y. Amount shown includes PEG4000 +      H.sub.2 O 1:1 by weight                                                        .sup.(g) Carbowax polyethylene glycol, 1300-1600 molecular weight, Mfg. b      Union Carbide Corporation, New York, N.Y. Amount shown includes PEG1540 +      H.sub.2 O 1:1 by weight                                                        .sup.(m) Carbowax polyethylene glycol, 380-420 molecular weight, Mfg. by       Union Carbide Corporation, New York, N.Y. Liquid at R/T, No H.sub.2 O          included in amounts shown above                                                OTHER NOTES  See Table I                                                 

                                      TABLE XIX                                    __________________________________________________________________________     PROPERTY VARIATIONS DUE TO USING OPTIMUM                                       AMOUNTS OF METHOXYPOLYETHYLENE GLYCOL                                          ADDITIVES OF DIFFERENT MOLECULAR WEIGHTS                                                             BASIC FORMULATION:                                                                            90.8g H.sub.2 O                                                                2.35g Isopropanol                                                              4.05g l-propanol                                                               0.364gNH.sub.4 OH.sup.(o)                                                      0.011g Surfactant BA-77.sup.(b)                                 MPEG-see below                                                                                24" ×18" Lubricity Test:Plate                                            Glass                                                           TEST SURFACE:  other tests single strength mirror           Methoxy -   Molecular                                                          Polyethylene                                                                          Amount                                                                              Weight                  Residual Contamination                                                                     Oil Removal Test            #  Glycol (grams)                                                                             Range Lubricity         (Clean Glass)                                                                              (1 Drop Wesson.sup.(R)                                                         Oil)                        __________________________________________________________________________                          Definitely more drag than CX-1                                                 nearly dry or completely dry,                             CX-7                                                                              MPEG-550.sup.(d)                                                                      0.06 525-575                                                                              slightly sticky feeling and chat-                                                                None        Clean Surface                                    tering when rubbing back and forth                                             with paper towel when dry                                                      ˜CX-1 when nearly dry but slightly                  CX-3                                                                              MPEG-2M.sup.(n)                                                                       0.16 1900  more drag completely dry                                                                         None        Clean Surface                                    Excellent-very low drag and                               CX-1                                                                              MPEG-5K.sup.(f)                                                                       0.20 5000  excellent transition, very                                                                       None        Clean Surface                                    slightly less drag than CW-1                                                   (Table XVIII)                                             __________________________________________________________________________      .sup.(d) Carbowax methoxypolyethylene glycol, 525-575 molecular weight,        Mfg. by Union Carbide Corporation, New York, N.Y. Liquid at R/T, no            H.sub.2 O included in amounts shown above                                      OTHER NOTES  See Table I                                                 

                                      TABLE XX                                     __________________________________________________________________________     CHEMICAL AND PHYSICAL PROPERTIES OF SELECTED                                   POLYETHYLENE AND METHOXYPOLYETHYLENE GLYCOLS                                                              Apparent                                                                       Specific     H.sub.2 O                                                                             Viscosity                                                                             Comparative                                 Molecular                                                                              Gravity                                                                               Freezing                                                                             Solubility                                                                            Centistoke                                                                            Hygroscopicity           Type               Weight Range                                                                           (20/20° C.)                                                                    Range % by Weight                                                                           at 210° F.                                                                     (Glycerin =              __________________________________________________________________________                                                           100)                     Carbowax           380-420 1.1281 4-8 C.                                                                               100%    7.3   60                       Polyethylene Glycol 400                                                        Carbowax                                                                       Polyethylene Glycol 600                                                                           570-630 1.1279 20-25 C.                                                                             100%   10.5   50                       Carbowax                                                                       Polyethylene Glycol 1000                                                                          950-1050                                                                               1.101  37-40 C.                                                                             ˜70%                                                                            17.4   35                       Carbowax                                                                       Polyethylene Glycol 1500                                                                          500-600 1.151  38-41 C.                                                                             73%    13-18  35                       Carbowax                                                                       Polyethylene Glycol 1540                                                                          1300-1600                                                                              1.0910 43-46 C.                                                                             70%    25-32  30                       Carbowax                                                                       Polyethylene Glycol 4000                                                                          3000-3700                                                                              1.204  53-56 C.                                                                             62%    80-95  --                       Carbowax                                                                       Polyethylene Glycol 6000                                                                          6000-7500                                                                              1.207  60-63 C.                                                                             ˜50%                                                                            700-900                                                                               --                       Carbowax                                                                       Polyethylene Glycol 20,000 linear                                                                 18000-19000                                                                            1.215  56 C. --     8,179  --                       Polyethylene Glycol                                                            Compound 20M       15000 approx.                                                                          1.207  50-55 C.                                                                             50%    14,500 --                       Carbowax                          -5 to                                        Methoxypolyethylene Glycol 350                                                                    335-365 1.094  +10 C.                                                                               100%    4.1   --                       Carbowax                   1.089                                               Methoxypolyethylene Glycol 550                                                                    525-575 (40/20° C.)                                                                    15-25 C.                                                                             100%    7.5   --                       Carbowax                   1.094                                               Methoxypolyethylene Glycol 750                                                                    715-785 (40/20° C.)                                                                    27-33 C.                                                                             100%   10.5   --                       Carbowax                                                                       Methoxypolyethylene Glycol 2000                                                                   1900    --     51.9 C.                                                                              --     54.6   --                       Carbowax                                                                       Methoxypolyethylene Glycol 5000                                                                   5000    --     59.2 C.                                                                              --     61.3   --                       __________________________________________________________________________      NOTE:                                                                          Data taken from Union Carbide "1975-1976 Chemical and Plastics Physical        Properties" Publications.                                                

Referring to Tables XVIII and XIX it can be seen that all of the molecular weight ranges tested provided excellent oil and grease repulsion regardless of whether the additive was polyethylene or methoxypolyethylene glycol. Also, when used in the preferred amounts, there was found to be no problem with residual streaking on the glass surface after wiping to the dry condition.

The primary differences between these polyethylene and methoxypolyethylene glycol additives is seen to occur in the degree of imparted lubricity during the time the liquid cleaner is being wiped from the surface with absorbent toweling. The data in this respect, shows that the superior choices are those of the higher molecular weight ranges that form hard, waxy, non-hygrosiopic solids at room temperature.

Those that are liquids at room temperature present more drag when nearly dry or completely dry than the former. Formulation CW-8, containing polyethylene glycol 1540, in Table XVIII is quite a soft waxy material at room temperature and occupies a relatively intermediate position from the lubricity standpoint.

Overall, there also appears to be little discernible advantage between the polyethylene and methoxypolyethylene glycols in similar molecular weight ranges.

The amount of each molecular weight grade of polyethylene or methoxypolyethylene glycol used in the examples of Tables XVIII and XIX were determined from prior tests to be the amount that maximized lubricity when applied to a plate glass surface and wiped dry with a paper towel. In every case, it was found that using higher or lower amounts of a given glycol would cause an increase in the overall frictional properties when the surface of the glass has been wiped to the nearly dry stage; however, when wiped to the completely dry stage, exceeding the optimum amount does not show any particular change in the drag properties.

By way of example, Table XXI shows the relative effects on lubricity by varying the amount of polyethylene glycol CARBOWAX 400 in a given formulation. Tables XXII and XXIII cover the same type of data for polyethylene glycol CARBOWAX 20,000 linear and methoxypolyethylene glycol CARBOWAX 5,000, respectively. Data for the other molecular weight grades has not been included because the overall effect is essentially the same and the optimized values are found in Tables XVIII and XIX.

                                      TABLE XXI                                    __________________________________________________________________________     EFFECT OF VARYING AMOUNTS OF CARBOWAX POLYETHYLENE                             GLYCOL - 400 ADDITIVE IN RESPECT TO OVERALL LUBRICITY                                                BASIC FORMULATION:                                                                          90.8g H.sub.2 O                                                                2.35 Isopropanol                                                               4.05 l-propanol                                                                0.364 NH.sub.4 OH.sup.(o)                                                      0.011 Surfactant BA-77.sup.(b)                                                 --PEG-400 see below                                               TEST SURFACE:                                                                               24" × 18" Plate Glass                                Amount                                                          #   Polyethylene Glycol                                                                       (grams)                                                                             Lubricity                                                  __________________________________________________________________________     CW-14                                                                              PEG-400.sup.(m)                                                                           0.068                                                                               Definitely more drag nearly dry and completely dry                             than CW-15                                                                     Low Drag - Definitely less drag nearly dry and better                          transition wet to dry                                      CW-15                                                                              PEG-400    0.102                                                                                     than CW-14 or CW-15                                                            When completely dry tends to squeak slightly                             when surface is rubbed                                                               back and forth with paper towel                      CW-16                                                                              PEG-400    0.136                                                                               A little more drag nearly dry than CW-15 and                                   ˜same when dry.                                                          More squeaking or chattering wet than CW-15 but                                ˜same dry.                                           __________________________________________________________________________      NOTES                                                                          See Tables I and XVIII                                                   

                                      TABLE XXII                                   __________________________________________________________________________     EFFECT OF VARYING AMOUNTS OF CARBOWAX                                          POLYETHYLENE GLYCOL 20,000 LINEAR ADDITIVE                                     IN RESPECT TO OVERALL LUBRICITY                                                                      BASIC FORMULATION:                                                                          90.85g H.sub.2 O                                                               6.10 Isopropanol                                                               0.16 l-propanol                                                                0.104 NH.sub.4 OH.sup.(p)                                                      0.10 NH.sub.4 HCO.sub.3                                                        0.012 Surfactant BX-78.sup.(c)                                                 --PEG-20K linear.sup.(j)                                                       see below                                                         TEST SURFACE:                                                                               24" × 18" Plate Glass                               Amount                                                           #  Polyethylene Glycol                                                                       (grams)                                                                             Lubricity                                                   __________________________________________________________________________     JJ-1                                                                              PEG-20K.sup.(j)                                                                           0.162                                                                               Definitely not enough PEG-20k linear material - fair                           amount of drag                                                 linear          nearly dry and completely dry                               JJ-2                                                                              PEG-20K.sup.(j)                                                                           0.216                                                                               Considerably less drag than JJ-1 nearly dry but                                slightly more drag                                             linear          than JJ-6. ˜JJ-3 Completely dry.                      JJ-6                                                                              PEG-20K.sup.(j)                                                                           0.243                                                                               Very slightly less drag than JJ-2 nearly dry and very                          slightly more drag                                             linear          than JJ-3 nearly dry ˜ JJ-3 completely dry            JJ-3                                                                              PEG-20K.sup.(j)                                                                           0.270                                                                               Excellent-Very low overall drag and excellent                                  transition wet to                                              linear          completely dry.                                             JJ-5                                                                              PEG-20K.sup.(j)                                                                           0.297                                                                               ˜JJ-6                                                    linear                                                                      JJ-4                                                                              PEG-20K.sup.(j)                                                                           0.324                                                                               ˜JJ-1 Nearly dry but ˜ JJ-3 completely                             dry.                                                           linear                                                                      __________________________________________________________________________      NOTES-                                                                         See Table I and XIII                                                     

                                      TABLE XXIII                                  __________________________________________________________________________     EFFECT OF VARYING AMOUNTS OF CARBOWAX METHOXY-                                 POLYETHYLENE GLYCOL 5000 ADDITIVE IN RESPECT                                   TO OVERALL LUBRICITY                                                                                 BASIC FORMULATION:                                                                          90.85g H.sub.2 O                                                               6.10 Isopropanol                                                               0.16 l-propanol                                                                0.104 NH.sub.4 OH.sup.(p)                                                      0.10 NH.sub.4 HCO.sub.3                                                        0.012 Surfactant BX-78.sup.(c)                                                 --MPEG-5K.sup.(f) see                                                          below                                                             TEST SURFACE:                                                                               24" × 18" Plate Glass                                       Amount                                                    #    Methoxy-Polyethylene Glycol                                                                    (grams)                                                                              Lubricity                                          __________________________________________________________________________     JK-3  MPEG-5K.sup.(f) 0.15  Not enough MPEG-5 - Fair amount of drag both                                   nearly dry and when                                                            completely dry                                     JK-31/2                                                                              MPEG-5K.sup.(f) 0.175 Definitely less drag than JK-3 nearly dry.                                     But slightly more drag                                                         than JK-4 nearly dry. ˜JK-4 completely                                   dry                                                JK-4  MPEG-5K.sup.(f) 0.20  Excellent-Lowest overall drag of series,                                       excellent transition wet                                                       to completely dry                                  JK-41/2                                                                              MPEG-5K.sup.(f) 0.225 ˜JK-31/2 Can't tell any difference           JK-5  MPEG-5K.sup.(f) 0.25  Considerably more drag than JK-4, nearly dry                                   but ˜ JK-4 when dry                          WINDEX                                                                               --              --    ˜ JK-4 and others when wet but more                                      drag than JK-3 nearly dry and                                                  considerably more drag when                        __________________________________________________________________________                                 dry.                                                NOTES                                                                          See Table I                                                              

A variety of tests have been conducted where more than one molecular weight grade of polyethylene or methoxypolyethylene glycol have been used in the same formulation. Also, combinations of these compounds in differing molecular weight grades have been similarly tried. While in many cases excellent results have been obtained, no particular advantage could be found in such combinations either from the lubricity, oil removal or anti-contamination standpoints.

The optimized amounts of the polyethylene and methoxypolyethylene glycols for a given molecular weight grade were found to remain fairly well fixed, at least for the cleaning of window and mirror surfaces, in spite of nominal variations in amount of ammonium hydroxide, or nominal amounts or types of inorganic or organic lubricants, surfactants, or grease cutters; however, drastically increasing the amount of alcohol in a particular formulation will necessitate a reduction in the amount of the polyethylene or methoxypolyethylene glycol required for optimum lubricity characteristics. This indicates that the water/glycol relationship is the important relationship and not simply the total liquid to polyethylene or methoxypolyethylene glycol ratio.

Some high alcohol content formulations are shown in Table XXIV. These have been designed for use at temperatures as low as the order of -40° F. without freezing, and utilize isopropanol, methanol, and in one formulation a combination of isopropanol and 1-propanol. Because of the drastic change in alcohol content some control samples were also included for reference purposes.

                                      TABLE XXIV                                   __________________________________________________________________________     HIGH ALCOHOL CONTENT FORMULATIONS FOR                                          LOW TEMPERATURE USE (˜-40F.)   BASIC FORMULATION- See Below                                                             24" × 18" Lubricity                                                      Test: Plate                                                                    Glass; other tests single                                            TEST SURFACE:                                                                            strength mirror                                                      Residual                                             Amount                    Contamination                                                                            Oil Removal Test                #   Formulation                                                                           (grams)                                                                             Lubricity            (Clean Glass)                                                                            (1 Drop 'WESSON                 __________________________________________________________________________                                                    Oil)                            CM-2                                                                               H.sub.2 O                                                                             85.7 ˜ CN-2         None      Very Clean                          Isopropanol                                                                           4.0  a little less drag than CN-1 and                                   1-propanol                                                                            6.3  a little more drag than CN-3 when                                  2,3-butanediol                                                                        0.026                                                                               nearly dry. same as CN-1 and                                       MPEG-5K.sup.(f)                                                                       0.20 CN-3 when dry                                                  CN-1                                                                               H.sub.2 O                                                                             53.0 A little more drag than CN-2                                                                        Very faint                                                                               No obvious oil                      Isopropanol                                                                           36.0 nearly dry but ˜ same dry.                                                                    streaks - streaks, but MPEG-5K                2,3-butanediol                                                                        0.026                     believed to be                                                                           as faint residual                   MPEG-5K.sup.(f)                                                                       0.20                      excess MPEG-5K                                                                           streaks still present           CN-2                                                                               H.sub.2 O                                                                             53.0 ˜ CM-2 Can't tell any                                                                         None      Very Clean                          Isopropanol                                                                           36.0 difference                                                         2,3-butanediol                                                                        0.013                                                                   MPEG-5K.sup.(f)                                                                       0.10                                                                CN-3                                                                               H.sub.2 O                                                                             53.0 Very slightly less drag than                                                                        None      Very Clean                          Isopropanol                                                                           14.5 CM-2 or CN-2 when nearly dry                                       1-propanol                                                                            24.75                                                                               ˜ same when dry                                              23-butanediol                                                                         0.013                                                                   MPEG-5K.sup.(f)                                                                       0.10                                                                CN-4                                                                               H.sub.2 O                                                                             49.1 Definitely more drag nearly dry                                                                     None      Very Clean                          Methanol                                                                              39.4 than CN-2 ˜CN-2 completely dry.                              2,3-butanediol                                                                        0.013                                                                               Not as smooth a transition wet                                     MPEG-5K.sup.(f)                                                                       0.10 to dry as CN-2                                                 CN-0                                                                               H.sub.2 O                                                                             53.0 Very great drag both nearly dry                                                                     None      Large amount oil                    Isopropanol                                                                           36.0 and completely dry OK wet. Very                                                                               streaking all over                              much more drag than CN-2 or CN-1                                                                              surface of glass                                nearly dry or completely dry.                                                  Very poor transition wet to dry                                CN-5                                                                               H.sub.2 O                                                                             49.1 ˜ CN-0         None      ˜ CN-0                        Methanol                                                                              39.4 Very much more drag than CN-4  Large amount oil                                nearly dry and when completely streaking all over                              dry                                                            __________________________________________________________________________

Referring to Table XXIV, Sample #CM-2 is a normal, low alcohol content formulation containing a mixture of isopropanol and 1-propanol. As will be noted this sample showed the expected excellent results in terms of lubricity, residual streaking and oil removal properties. Sample #CN-1 is very similar to #CM-2 except that it contains a very high percentage of isopropanol. The data shows that this caused a little higher drag than #CM-2 but more significantly caused residual streaking that was just beginning to show up on the glass surface after wiping to the dry stage. This streaking was undoubtedly due to the excess methoxypolyethylene glycol that was now present in the formulation since the water content had been very considerably reduced due to the high alcohol addition.

This latter problem is seen to have been completely eliminated in sample #CN-2 where the only change from #CN-1 has been to cut the amounts of the organic lubricant and the methoxypolyethylene glycol in half. The low drag characteristic has also been restored to that of the #CM-2 formulation with the lower alcohol content. Sample #CN-3 was also run where the higher alcohol content was composed of both isopropanol and 1-propanol and included the reduced methoxypolyethylene glycol amount. Again, excellent results were obtained.

Sample #CN-4 is very similar to #CN-2 except that methanol has been substituted for isopropanol. As can be seen in Table XXIV, the methanol degraded the overall lubricity of the formulation over that of using isopropanol. This confirms the data obtained earlier in Table II, where smaller, more normal amounts of methanol were compared with isopropanol on a lubricity basis.

Formulations #CN-0 and #CN-4 containing isopropanol and methanol, respectively, but having neither polyethylene or methoxypolyethylene glycol as an additive, were included to confirm that is spite of the high alcohol content the overall lubricity and excellent oil contamination removal properties are now absent.

High alcohol content formulations, such as those just described, are suitable for use in the liquid storage reservoirs for automobile and truck window cleaner systems where winter freezing can be a problem. In applications of this type, where the wiping operation is not being done by hand, a formulation possessing maximized lubricity characteristics may not be important. For example, formulation #CN-4 of Table XXIV containing methanol, has been found to provide excellent cleaning results in just such an application. In uses of this type, for example #CN-4 of Table XXIV, the methanol is usually less costly as well as providing a lower freezing point for the amount added than the other higher boiling point alcohols.

In summarizing, it can be stated that all of the polyethylene and methoxypolyethylene glycol molecular weight grades referred to in the tables of this application have been found to provide liquid cleaning solutions possessing excellent lubricity and extremely good oil and grease removal properties.

A preferred grouping of these polyethylene and methoxypolyethylene glycol compounds can be made by selecting the higher molecular weight grades. Such a group could consist of the polyethylene glycol CARBOWAX 4,000, 6,000, 20,000 linear, polyethylene glycol compound 20M and methoxypolyethylene glycol CARBOWAX 2,000, 5,000. Other and higher molecular weight compounds that are non-hygroscopic, if available, would appear to be satisfactory.

It should be pointed out that the CARBOWAX polyethylene glycol compound 20M material manufactured by Union Carbide Corporation is reported to be a cross-linked 6,000 molecular weight polyethylene glycol. In this respect it differs from the linear, long chain molecular structure of the other polyethylene and methoxypolyethylene glycols.

Referring to Table XX it can also be seen that the polyethylene glycol 20M material has a considerably higher viscosity value than any of the other grades.

Tests have been made with the liquid cleaning solutions of this invention in order to optimize the liquid flow on the surface being cleaned. This property is, of course, affected by the alcohol content and the particular type and amount of surfactant used. It has also been found that the particular grade of polyethylene glycol or methoxypolyethylene glycol employed in the formulation can have a considerable effect on this property.

For example, referring to Table XXV, formulation JX-13 containing CARBOWAX polyethylene glycol 20,000 linear material was found to provide noticeablly better wetting of a polished LUCITE surface than formulation JX-14 containing CARBOWAX polyethylene glycol 6,000 or formulation JX-11 containing methoxypolyethylene glycol 5,000. Furthermore, the polyethylene glycol compound 20M grade used in formulation JX-10 reduced the surface tension to an even greater extent under the same test conditions.

                                      TABLE XXV                                    __________________________________________________________________________     REPRESENTATIVE FORMULATIONS FOR WINDOW,                                        MIRROR, GLASS AND CHROME CLEANERS FOR                                          GENERAL HOUSEHOLD USE                                                              H.sub.2 O Grease                                                               and  Amount                                                                              Cutting  Amount                                                                              Organic                                                                              Amount     Amount                                                                              PEG or  Amount               #   Alcohol                                                                             (grams)                                                                             Aids     (grams)                                                                             Lubricant                                                                            (grams)                                                                             Surfactant                                                                           (grams)                                                                             MPEG    (grams)              __________________________________________________________________________     JX-10                                                                              H.sub.2 O                                                                           86.75                                                                               NH.sub.4 OH.sup.(p)                                                                     0.104                                                                               None  --   BX-78.sup.(c)                                                                        0.012                                                                               PEGC-20M.sup.(i)                                                                       0.26                     Iso- 9.45 NH.sub.4 HCO.sub.3                                                                      0.08                                                        propanol  K.sub.2 B.sub.4 O.sub.7 . 4H.sub.2 O                                                    0.10                                                        1-   0.344                                                                     propanol                                                                   JX-11                                                                              H.sub.2 O                                                                           86.75                                                                               NH.sub.4 OH.sup.(p)                                                                     0.104                                                                               None  --   BX-78.sup.(c)                                                                        0.012                                                                               MPEG-5K.sup.(f)                                                                        0.20                     Iso- 7.45 NH.sub.4 HCO.sub.3                                                                      0.08                                                        propanol  K.sub.2 B.sub.4 O.sub.7 . 4H.sub.2 O                                                    0.10                                                        1-   0.244                                                                     propanol                                                                   JX-12                                                                              H.sub.2 O                                                                           86.75                                                                               NH.sub.4 HCO.sub.3                                                                      0.08 None  --   BX-78.sup.(c)                                                                        0.012                                                                               PEGC-20M.sup.(i)                                                                       0.26                     Iso- 9.45 KBO.sub.2 . ×  H.sub.2 O                                                          0.1                                                         propanol                                                                       1-   0.244                                                                     propanol                                                                   JX-13                                                                              H.sub.2 O                                                                           86.75                                                                               NH.sub.4 OH.sup.(p)                                                                     0.104                                                                               None  --   BX-78.sup.(c)                                                                        0.012                                                                               PEG-20,000.sup.(j)                                                                     0.27                     Is-  9.45 NH.sub.4 HCO.sub.3                                                                      0.08                       linear                           propanol  K.sub.2 B.sub.4 O.sub.7 . 4H.sub.2 O                                                    0.10                                                        1-   0.244                                                                     propanol                                                                   JX-14                                                                              H.sub.2 O                                                                           86.75                                                                               NH.sub.4 OH.sup.(p)                                                                     0.104                                                                               none  --   BX-78.sup.(c)                                                                        0.012                                                                               PEG-6000.sup.(h)                                                                       0.20                     Iso- 9.45 NH.sub.4 HCO.sub.3                                                                      0.08                                                        propanol  K.sub.2 B.sub.4 O.sub.7 . 4H.sub.2 O                                                    0.10                                                        1-   0.244                                                                     propanol                                                                   GA-8                                                                               H.sub.2 O                                                                           90.80                                                                               NH.sub.4 OH.sup.(p)                                                                     0.260                                                                               2,3   0.026                                                                               BA-77.sup.(b)                                                                        .011 MPEG-5K.sup.(f)                                                                        0.20                     Iso- 2.35 NH.sub.4 HCO.sub.3                                                                      0.075                                                                               butanediol                                             propanol                                                                       1-   4.06                                                                      propanol                                                                   GA-10                                                                              H.sub.2 O                                                                           83.50                                                                               NH.sub.4 OH.sup.(p)                                                                     0.26 3-    0.123                                                                               BA-77.sup.(b)                                                                        .011 PEG-6000.sup.(h)                                                                       0.20                     Iso- 4.65               Methoxy,                                               propanol           1 -                                                         1-   6.50               butanol                                                propanol                                                                   JY-37                                                                              H.sub.2 O                                                                           88.60                                                                               NH.sub.4 OH.sup.(p)                                                                     0.156                                                                               none  --   BX-78.sup.(c)                                                                        0.012                                                                               PEGC-20M.sup.(i)                                                                       0.26                     Iso- 7.80 (NH.sub.4).sub.2 CO.sub.3                                                               0.10                                                        propanol                                                                       1-   0.201                                                                     propanol                                                                   KB-18                                                                              H.sub.2 O                                                                           86.75                                                                               NH.sub.4 OH.sup.(p)                                                                     0.21 1,3   0.31 BL-225.sup.(a)                                                                       0.013                                                                               MPEG-5K.sup.(f)                                                                        0.20                     Iso- 9.45               butanediol                                             propanol                                                                       1-   0.244                                                                     propanol                                                                   JY-34                                                                              H.sub.2 O                                                                           85.90                                                                               NH.sub.4 OH.sup.(p)                                                                     0.156                                                                               none  --   BX-78.sup.(c)                                                                        0.012                                                                               MPEG-5K.sup.(f)                                                                        0.20                     Iso- 10.00                                                                               Na.sub.3 PO.sub.4 . 12H.sub.2 O                                                         0.075                                                       propanol                                                                            0.258                                                                               NH.sub.4 HCO.sub.3                                                                      0.08                                                        1-   0.258                                                                     propanol                                                                   KB-8                                                                               H.sub.2 O                                                                           86.75                                                                               NH.sub.4 OH.sup.(p)                                                                     0.156                                                                               2,3-  0.039                                                                               BX-78.sup.(c)                                                                        0.012                                                                               PEGC-20M.sup.(i)                                                                       0.26                     Iso- 9.45               butanediol                                             propanol                                                                       1-   0.244                                                                     propanol                                                                   KB-11                                                                              H.sub.2 O                                                                           86.75                                                                               NH.sub.4 OH.sup.(p)                                                                     0.156                                                                               2,3-  0.039                                                                               BX-78.sup.(c)                                                                        0.012                                                                               MPEG-5K.sup.(f)                                                                        0.2                      Iso- 9.45               butanediol                                             propanol                                                                       1-   0.244                                                                     propanol                                                                   KB-14                                                                              H.sub.2 O                                                                           86.75                                                                               NH.sub.4 OH.sup.(p)                                                                     0.156                                                                               2,3-  0.026                                                                               BX-78.sup.(c)                                                                        0.012                                                                               MPEG-5K.sup.(f)                                                                        0.2                      Iso- 9.45 NH.sub.4 HCO.sub.3                                                                      0.08 butanediol                                             propanol  K.sub.2 B.sub.4 O.sub.7 . 4H.sub.2 O                                                    0.1                                                         1-   0.244                                                                     propanol                                                                   KB-15                                                                              H.sub.2 O                                                                           86.75                                                                               NH.sub.4 OH.sup.(p)                                                                     0.11 2,3-  0.026                                                                               BX-78.sup.(c)                                                                        0.012                                                                               MPEG-5K.sup.(f)                                                                        0.2                      Is-  9.45 NH.sub.4 HCO.sub.3                                                                      0.08 butanediol                                             propanol  KBO.sub.2 .× H.sub.2 O                                                            0.1                                                         1-   0.244                                                                     propanol                                                                   __________________________________________________________________________      .sup.(a) ANTAROX surfactant, modified linearaliphatic polyether, Mfg. by       GAF Corporation, New York, N.Y.                                                OTHER NOTES  See Tables I and XIII                                       

Minimizing the surface tension may be of particular importance when the liquid cleaning solutions are to be used on oil and grease contaminated or other hard to wet surfaces.

Table XXV lists a number of examples of liquid window, mirror and glass cleaners for general household use. All of these formulations have been found to provide exceptionally good transfer of oil, grease and other contaminants from the glass surface to the absorbent toweling. They have all shown very low frictional resistance between the toweling and the glass surface during the drying operation. They have also shown excellent resistance to re-contamination by airborne hydrocarbons. This property will be described later.

While the main emphasis in this application has been for the use of this invention for the cleaning of windows, mirrors and glass surfaces, it has been found that many of the formulations, including those in Table XXV, have other important uses. For example, these formulations have been found to be very effective for polishing and cleaning hard chrome plated objects, stainless steel and enameled surfaces, glazed ceramics, FORMICA countertops, a variety of plastics, and many other smooth surfaces.

The same oil and grease transferring properties desired for cleaning windows and mirrors are often of equal importance in these other cleaning areas. Chrome plated faucets and fixtures are extremely easy to clean to a high luster with the polyethylene or methoxypolyethylene glycol containing formulations without leaving oil, grease or soap streaks. Brushed stainless steel counter and stove tops can be easily wiped clean of grease splatters without re-distributing the contaminating material as visible streaks.

For specialized cleaning jobs of the type just described, and where the extreme optical clarity required for cleaning window and mirror surfaces may not be necessary, larger amounts of polyethylene or methoxypolyethylene glycol additives can often be tolerated or may even be advantageous.

Table XXVI shows formulations of this type designed for cleaning FORMICA table and countertops, and the like, where it is desired to not only efficiently remove oil, grease and other surface contamination but to also leave a visible wax sheen on the cleaned surface. As can be seen from the table, the amounts of the methoxypolyethylene and polyethylene glycols used in formulations LD-3, LD-4, LD-5 and LD-7 range from twice to slightly more than three times the amounts that would be used for optimum lubricity and optical clarity in a comparable formulation for cleaning mirrors and windows.

                                      TABLE XXVI                                   __________________________________________________________________________     HIGH POLYETHYLENE OR METHOXYPOLYETHYLENE                                       CONTAINING FORMULATIONS FOR SPECIAL CLEANING                                   APPLICATIONS                                                                                                Or-                                                                            ganic                                                 H.sub.2 O and                                                                         Amount                                                                             Grease    Amount                                                                             Lu- Amount                                                                              Sur- Amount                                                                              PEG or                                                                              Amount                    #   Alcohol                                                                               (grams)                                                                            Cutting Aids                                                                             (grams)                                                                            bricant                                                                            (grams)                                                                             factant                                                                             (grams)                                                                             MPEG (grams)                   __________________________________________________________________________     LD3 H.sub.2 O                                                                             90.80                                                                              (NH.sub.4).sub.2 CO.sub.3                                                                0.1g                                                  LD3 Isopropanol                                                                           2.35                                                                               KBO.sub.2 . x H.sub.2 O                                                                  0.1g                                                                               none                                                                               --   BA-77.sup.(b)                                                                       .028 MPEG-                                                                               0.40                          1-propanol                                                                            4.05                                 5K.sup.(f)                     LD-4                                                                               H.sub.3 O                                                                             86.75                                                                              NH.sub.4 HCO.sub.3                                                                       0.1g                                                      Isopropanol                                                                           9.45                                                                               Na.sub.3 C.sub.6 H.sub.5 O.sub.7 . 2H.sub.2 O                                            0.3g                                                                               none                                                                               --   BX-78.sup.(c)                                                                       .024 PEGC-                                                                               0.52                          1-propanol                                                                            0.244                                20M.sup.(i)                    LD-7                                                                               H.sub.2 O                                                                             86.60                                                                              NH.sub.4 HCO.sub.3                                                                       0.1g                   PEG-                               Isopropanol                                                                           7.80                                                                               Na.sub.3 PO.sub.4                                                                        0.1g                                                                               none                                                                               --   FC-98.sup.(q)                                                                       .02  20,000.sup.(j)                                                                      0.81                          1-propanol                                                                            0.203                                linear                         LD-5                                                                               H.sub.2 O                                                                             88.60                                                                              NH.sub.4 OH.sup.(p)                                                                      .364                                                      Isopropanol                                                                           7.80              2,3 0.078                                                                               BX-78                                                                               .024 PEGC-                                                                               0.52                          1-propanol                                                                            0.203             buta-              20M.sup.(i)                                                 nediol                                            __________________________________________________________________________      .sup.(q) FLUORAD surfactantpotassium perfluoroalkyl sulfonate, Mfg. by 3M      Co., St. Paul, Minnesota                                                       OTHER NOTES  See Tables I and XIII                                       

It will also be noted that greater amounts of added grease-cutting aids have been used in some of these specialized cleaners. Formulation LD-4, for example, uses sodium citrate in an amount that would cause a cloudy appearance on a glass surface under high humidity conditions; however, a slight contamination of this type will be unnoticed in the intended application and consequently the excellent oil and grease-cutting properties found to be present with the addition of the citrate can be exploited.

One of the important advantages of using the polyethylene or methoxypolyethylene glycol additive in the window and mirror cleaning solutions as practiced in this invention, is their ability to maintain the glass surface in a clean condition.

More specifically, the residual layer of the polyethylene or methoxypolyethylene glycol that is left on the surface following the cleaning and drying operation has been found to be extremely resistant to re-contamination by airborne hydrocarbons.

This unique property is due to a combination of the inherent oil and grease repelling properties of the polyethylene or methoxypolyethylene glycol compounds coupled with an extremely low evaporation rate. In this latter respect, it has been found that the lower molecular weight CARBOWAX polyethylene glycol 400 and methoxypolyethylene glycol 550 grades, when spread as a thin layer on a glass surface, where still visible after 60 days (at which time the test was discontinued). Thin films of the higher molecular weight materials appear to be extremely long lasting.

A convenient means of testing this anti-contaminating property has involved cleaning the inside front and rear windows of a Karmann Ghia automobile. A variety of formulations of this invention have been directly compared in this manner with a number of commercial liquid window cleaning products. These are listed in Table XXVII.

                                      TABLE XXVII                                  __________________________________________________________________________     FORMULATIONS USED IN AIRBORNE HYDROCARBON                                      CONTAMINATION COMPARISON TESTS ON AUTOMOBILE                                   INTERIOR WINDOW SURFACES                                                       TEST SURFACE: Inside Karmann Ghia Front                                        Windshield & Rear Window                                                           Commercial                                                                     Cleaner or  Grease Cutting         PEG         Test Duration                   H.sub.2 O and                                                                         Amount                                                                              Aids and/or                                                                            Amount                                                                              Sur- Amount                                                                              or MPEG                                                                               Amount                                                                              and                         #   Alcohol                                                                               (grams)                                                                             Lubricant                                                                              (grams)                                                                             factant                                                                             (grams)                                                                             Additive                                                                              (grams)                                                                             Surface                     __________________________________________________________________________                                                        Condition                   W-1 WINDEX --   --      --   --   --   --     --   3-14 days                                                                      Visually cloudy                                                                surface                     G-P GLASS PLUS                                                                            --   --      --   --   --   --     --   ˜W-1                  A   AJAX   --   --      --   --   --   --     --   ˜W-1                  E-O EASY OFF                                                                              --   --      --   --   --   --     --   ˜W-1                  S   SPARKLE                                                                               --   --      --   --   --   --     --   ˜W-1                  BA  BON-AMI                                                                               --   --      --   --   --   --     --   11 Days                                                                        Visually cloudy                                                                surface                     W-2 WINDEX --   --      --   --   --   --     --   3-8 Weeks, Severe                                                              surface clouding,                                                              vision impaired             GP-2                                                                               GLASS  --   --      --   --   --   --     --   3-6 Weeks                       PLUS                                           W-2                             H.sub.2 O                                                                             78.65                                                                               --      --   BA-77.sup.(b)                                                                       0.01 PEG-6K.sup.(h)                                                                        0.15 3 Weeks, Still clear        1                                                  no visual impairment            Isopropanol                                                                           15.65                                                                   H.sub.2 O                                                                             81.1 --      --   BA-77.sup.(b)                                                                       0.006                                                                               PEG-6K.sup.(h)                                                                        0.2  8 Days, Very Clear              Isopropanol                                                                           13.69                                                                   H.sub.2 O                                                                             83.75                                                               D               --      --   BA-77.sup.(b)                                                                       0.006                                                                               PEG-6K.sup.(h)                                                                        0.35 10 Days ˜B                Isopropanol                                                                           11.75                                                                   H.sub.2 O                                                                             83.75                                                               E               NH.sub.4 OH.sup.(o)                                                                    0.36 BA-77.sup.(b)                                                                       0.006                                                                               PEG-6K.sup.(h)                                                                        0.35 11 Days ˜B                Isopropanol                                                                           11.75                                                                   H.sub.2 O                                                                             92.32                                                               F   Isopropanol                                                                           2.80 NH.sub.4 OH.sup.(o)                                                                    0.21 BA-77.sup.(b)                                                                       0.006                                                                               MPEG-5K.sup.(f)                                                                       0.2  9 Days ˜B                 butyl                                                                          cellosolve                                                                     H.sub.2 O                                                                             88.65                                                                               NA.sub.4 P.sub.2 O.sub.7 .                                                     10H.sub.2 O                                                                            0.05                                                   O                            FC-95.sup.(q)                                                                       0.004                                                                               MPEG-5K.sup.(f)                                                                       0.2  3 Days ˜B                 Isopropanol                                                                           8.17 Na.sub.2 CO.sub.3 .                                                            10H.sub.2 O                                                                            0.1                                                                    NH.sub.4 OH.sup.(o)                                                                    0.26                                                       H.sub.2 O                                                                             88.65                                                                               Na.sub.2 B.sub.4 O.sub.7 .                                                     10H.sub.2 O                                                                            0.2                                                    L                            FC-95.sup.(q)                                                                       0.-04                                                                               MPEG-5K.sup.(f)                                                                       0.2  3 Days ˜B                 Isopropanol                                                                           8.17 Na.sub.2 CO.sub.3 . -                                                                            10H.sub.2 O                                                                         0.1                                         H.sub.2 O                                                                             88.65                                                                   Isopropanol                                                                           8.17              BL-225.sup.(a)                                                                      .014                                         J   3-Methoxy, 1-                                                                              NH.sub.4 OH.sup.(o)                                                                    0.26           MPEG-5K.sup.(f)                                                                       0.2  6 Days ˜B                 Butanol                                                                               0.16              FC-98.sup.(q)                                                                       .005                                             H.sub.2 O                                                                             83.65                                                               95  Isopropanol                                                                           5.84 NH.sub.4 OH.sup.(o)                                                                    0.36 BA-77.sup.(b)                                                                       0.006                                                                               MPEG-5K.sup.(f)                                                                       0.2  3 Weeks ˜1                1-propanol                                                                            6.09                                                                    H.sub.2 O                                                                             83.65                                   8 Weeks some surface            Isopropanol                                                                           5.84                                    deposit noticeable by       AK  1-propanol                                                                            6.09 NH.sub.4 OH.sup.(o)                                                                    0.36 BA-77.sup.(b)                                                                       0.006                                                                               MPEG-5K.sup.(f)                                                                       0.2  rubbing finger on                                                              glass                           3 Methoxy, 1-                                  but no real visual                                                             im-                             butanol                                                                               0.16                                    pairment                        H.sub.2 O                                                                             85.7                                                                    Isopropanol                                                                           4.0  NH.sub.4 OH.sup.(p)                                                                    0.26                                                   GA-11                                                                              1-propanol                                                                            6.3               BA-77.sup.(b)                                                                       0.011                                                                               PEG-20K.sup.(j)                                                                       0.27 2 Weeks ˜1                2,3-butanediol                                                                        0.026                                                                               NH.sub.4 HCO.sub.3                                                                     0.075          linear                                      H.sub.2 O                                                                             85.9 NH.sub.4 OH.sup.(p)                                                                    0.21                                                   JR-12                                                                              Isopropanol                                                                           10.0 NH.sub.4 HCO.sub.3                                                                     0.08 BX-78.sup.(c)                                                                       0.012                                                                               PEGC-20M.sup.(i)                                                                      0.26 2 Weeks ˜1                1-propanol                                                                            0.26 KBO.sub.2 . x H.sub.2 O                                                                0.1                                                        H.sub.2 O                                                                             86.75                                                                               NH.sub.4 OH.sup.(p)                                                                    0.104                                                  JX-10                                                                              Isopropanol                                                                           9.45 NH.sub.4 HCO.sub.3                                                                     0.08 BX-78.sup.(c)                                                                       0.012                                                                               PEGC-20M.sup.(i)                                                                      0.26 6 Weeks ˜AK               1-propanol                                                                            0.244                                                                               K.sub.2 B.sub.4 O.sub.7 . 4H.sub.2 O                                                   0.10                                                       H.sub.2 O                                                                             86.75                                                                               NH.sub.4 OH.sup.(p)                                                                    0.156                                                      Isopropanol                                                                           9.45 NH.sub.4 HCO.sub.3                                                                     0.08                                                   KB-14                                                                              1-propanol                                                                            0.244                                                                               K.sub.2 B.sub.4 O.sub.7 . 4H.sub.2 O                                                   0.1  BX-78.sup.(c)                                                                       0.012                                                                               MPEG-5K.sup.(f)                                                                       0.2  6 Weeks ˜AK               2,3 butanediol                                                                        0.026                                                               __________________________________________________________________________      NOTES                                                                          See Tables I, XIII, XXV and XXVI                                         

The testing procedure consisted simply of cleaning half of the window (such as the right side) with the commercial product and the other half with a polyethylene or methoxypolyethylene glycol containing formulation. The comparison was made by noticing differences in clarity due to "fogging" caused by hydrocarbon build-up on the inside window surfaces.

The results of these tests were found to be essentially identical in every instance. Namely, the half of the window cleaned with the commercial product began to show very definite signs of clouding or "fogging" in at least a weak's time. In hot weather this often occurred in as little as two days' time. In some instances, the test duration was five to eight weeks in length, at which point the contaminating film build-up on the half cleaned with the commercial window cleaning product was often found to be seriously affecting vision, especially at night with oncoming headlights. In all these direct comparison tests as can be seen in Table XXVII, the half cleaned with one of the polyethylene or methoxypolyethylene glycol containing formulations was always found to be remarkably free from any clouding effects or visual impairment.

These tests were conducted mainly during warm to hot weather and at an elevation of slightly over 7,000 feet. It is suspected that plasticizer outgasing from the interior of the automobile in addition to airborne oil and smoke particles was contributing to the rapid contamination rates noted with the commercial cleaners; however, the test data was felt to be relative in nature and is believed to correctly show the inherent contamination repelling nature of the formulations of this invention.

In this application, all percentages are by weight unless otherwise specified. Deionized water was used in the majority of the formulations included in this application. Tap water of reasonable softness has also been used in many instances, however, with no noticeable degradation of overall properties.

In my copending U.S. Patent Application, Ser. No. 885,311, now U.S. Pat. No. 4,213,873 of which this application is a continuation-in-part, the use of poly and/or methoxpolyethylene glycols have been shown to be of use as effective additives in water based window glass and chrome cleaner compositions. When employed in properly compounded formulations, these glycol additives have been found to provide specific advantages over competitive cleaners.

When used to clean glass or other hard, non-porous surfaces, these additives have been found to provide improved lubricity while wiping the surface during the wet to dry stage with appropriate toweling. Their use has also been found to provide a marked improvement in the transferral of oil and grease surface contamination to the toweling. In addition, the extremely thin transparent residual film or coating left on the surface has been found to repel effectively, for long periods of time, airborne organic contaminants. For example, inside windows of automobiles can be kept visually clear of oil and plasticizer fumes, using the formulations containing the poly or methoxypolyethylene glycols, for very long time periods as compared to conventional cleaners.

My copending application covered the use of polyethylene glycol and/or methoxypolyethylene glycol additives in the molecular weight range of about 400 to 20,000. The lower molecular weight materials are heavy liquids while the more preferred molecular weight additives of about 2000 and higher are wax like materials at room temperatures.

Polyethylene glycol can be expressed using the chemical formula:

    HOCH.sub.2 (CH.sub.2 OCH.sub.2).sub.n CH.sub.2 OH

For further clarification, a polyethylene glycol having a molecular weight of abot 20,000, the value of "n" in the above formula would be about 453. For a molecular weight of about 6000 "n" would equal about 135 and a molecular weight of about 400 would mean an "n" value of about 8.

Methoxypolyethylene glycol can be expressed using a similar formula but with the two HOCH₂ end groups replaced with H₃ CO groups as follows:

    H.sub.3 CO(CH.sub.2 OCH.sub.2).sub.n OCH.sub.3

Polyethylene glycols and methoxypolyethylene glycols are the only two such categories of materials being commercially produced at this time in the United States and were the two variations evaluated in the prior application.

It will be readily apparent to organic chemists, and others skilled in the art, that alkyl derivatives of polyethylene glycol, in addition to the methylpolyethylene glycol can be prepared, and that these would also be expected to perform in a similar fashion in these liquid cleaner formulations. Such alkyl derivatives would include: ethoxy, butoxy, pentoxy, and the like. These would have related chemical formulas to that of the methoxypolyethylene glycol except for the appropriate change in the two end groups.

The long chain central (CH₂ OCH₂)_(n) structure common to all these poly or alkoxypolyethylene glycol compounds is undoubtedly the major contributor to their excellent lubricating and oil and grease repelling properties when incorporated in the cleaner compositions. Changing the end alkyl groups from one to another would be expected to have little operational effect.

It is my present purpose to show that my invention in addition to covering the use of polyethylene glycols and the single alkyl derivative of methoxypolyethylene glycols includes the use of alkyl derivatives of polyethylene glycol and teaches the use of the more general designation of polyethylene glycols and their alkyl derivatives (or alkoxypolyethylene glycols). For this reason, a sample of butoxypolyethylene glycol was prepared for evaluation. This was made in the University of Colorado, Colorado Springs, Colo., using a conventional substitution method and was accomplished as follows, starting with a 4000 molecular weight polyethylene glycol:

Polyethylene glycol was converted to the disodium salt using metallic sodium.

Reaction with 1-brombutane affored the butoxypolyethylene groups as shown below:

    CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 Br+NaOCH.sub.2 (CH.sub.2 OCH.sub.2).sub.n CH.sub.2 ONa→CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 (CH.sub.2 OCH.sub.2).sub.n CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 +2NaBr

The resulting butoxypolyethylene glycol compound was crystallized and analyzed by 100 MHz fourier transform high resolution proton NMR spectroscopy and the existence of the terminal butyl groups verified. A control sample of the commercially obtained methoxypolyethylene glycol having a molecular weight of 2000 was similarly verified as being the methoxy compound.

As would be expected, the butoxypolyethylene glycol, prepared from the 4000 molecular weight polyethylene glycol was amost identical to the latter in physical properties, both being hard wax like solids at room temperature as well as being easily dissolved in water.

Comparison tests were then made to determine if any difference could be seen between the use of polyethylene glycol, methoxypolyethylene glycol and the butoxypolyethylene glycol. Test procedures were the same as those used in the copening application and were run using plate glass. Table XXVIII shows the specific cleaner formulations used and the results obtained. The data shows no discernable difference between the three formulations as far as lubricity, residual contamination and oil removal is concerned. These three formulations were subsequently used to clean naturally contaminated windows and again no difference in cleaning properties were noticed. All three formulations performed equally well with the overall conclusion that alkyl derivatives of polyethylene glycol can be used as effectively as polyethylene glycols and that the invention need not be limited to the use of the methoxypolyethylene glycol alone.

                                      TABLE XXVIII                                 __________________________________________________________________________     COMPARISON TESTS BETWEEN POLY, METHOXY AND BUTOXY                                                                        Basic  86.75 g H.sub.2 O             POLYETHYLENE GLYCOLS OF SIMILAR MOLECULAR WEIGHT                                                                         Formulation:                                                                          9.49 g isopropanol                                                             0.245 g n-propanol                                                             --g glycol-see below                                                           0.026 g 2,3-butanediol                                                         0.08 g                                                                         NH.sub.4 HCO.sub.3                                                             0.1 g Na.sub.3 PO.sub.4                                                        . 12H.sub.2 O                                                                  0.156g NH.sub.4 OH.sup.4                                                       (P)                                                                            0.012g Surfactant                                                              BX-78.sup.(c)                                     Lubricity                                                                               Test Surface: 24" × 18" Plate Glass                   Amount                                                                              Glycol                                                                              Wet to Nearly                                                                           Lubricity                                                                               Residual Contamination                                                                     Oil Removal Test             #  Glycol (Grams)                                                                             Mol. Wt.                                                                            Dry Stage                                                                               Dry Stage                                                                               (Clean Glass)                                                                              (1 Drop WESSON               __________________________________________________________________________                                                       OIL)                         NJ-1                                                                              Polyethylene                                                                          0.176                                                                               ˜4000                                                                         very low drag                                                                           very low drag                                                                           none        exceptionally clean,            Glycol                                         no oil streaks                                                                 remaining                       PEG-4000.sup.(e)                                                            NJ-2                                                                              Methoxy                                                                               0.2  ˜5000                                                                         ˜NJ-1                                                                             ˜NJ-1                                                                             none        ˜NJ-1                     Polyethylene                                                                   Glycol                                                                         MPEG-5K.sup.(f)                                                             NJ-3                                                                              Butoxy 0.21 ˜4000                                                                         ˜NJ-1 and NJ-2                                                                    ˜NJ-1 and NJ-2                                                                    none        ˜ NJ-1 and NJ-2           Polyethylene     no noticeable                                                                           no noticeable        no noticeable                   Glycol           difference in                                                                           difference in        difference in                                    repeated tests                                                                          repeated tests       repeated                     __________________________________________________________________________                                                       tests                         *FOR NOTES SEE TABLES I and XVIII                                        

Another important development relating to my copening application, Ser. No. 885,311 for water based window, glass and chrome cleaner composition has been made. This involves the use of triethylene glycol in place of the considerably higher molecular weight poly or methoxypolyethylene glycols of the prior work.

As described earlier, the poly or alkoxypolyethylene glycols, when employed in the cleaner formulation, leave a long lasting and normally transparent coating on glass and other surfaces following their proper application. This thin residual coating is extremely helpful in preventing subsequent airborne hydrocarbon contamination for long periods of time.

The cleaner formulations of the type using poly or alkoxypolyethylene glycols can be improperly used, however, so that an occasional cloudy or steaked area may result. Such misuse occurs, or at least becomes noticeable principally when cleaning glass windows, doors or mirrors with particularly large surface areas, and results from failure of the user to wipe off a portion of the sprayed on liquid with the toweling. When a heavy layer of the liquid cleaner is left to dry without wiping, the residual glycol layer that remains is often hard to remove without re-wetting with a damp towel.

The substitution of triethylene glycol for the considerably lower vapor pressure and higher molecular weight poly and alkoxypolyethylene glycols in otherwise similar cleaner formulations has been found to solve this misuse problem effectively. Repeated tests have shown that the triethylene glycol will evaporate rapidly following the wiping off of the cleaner solution with the toweling. Even heavy residual amounts of the cleaner inadvertently left on a glass surface will soon vaporize, leaving no trace of the glycol.

While the long term recontamination prevention properties are sacrificed by the fairly rapidly evaporating triethylene glycol, its use may be warranted and beneficial in cleaner compositions where reasonable care in its application may be expected to be lacking.

Triethylene glycol can be expressed using the chemical formula HOCH₂ (CH₂ OCH₂)₂ CH₂ OH and will be seen to be in reality a shorter molecular length form of polyethylene glycol. It has a molecular weight of 150, a vapor pressure of less than 0.01 mm at 20 C and a boiling point of 287.4 C. In addition, triethylene glycol has low toxicity, making it an excellent choice for a product of this type.

Many other organic compounds have been evaluated, using optimized amounts, for possible use as more rapidly evaporating replacements for the poly or alkoxypolyethylene glycols. While some of these provided varying degrees of lubricity and oil and grease transfer properties, none approached the triethylene glycol from an overall comparison standpoint. Among the organics evaluated were:

3-methoxybutanol, 1,3-propylene glycol, diethylene glycol monobutyl ether, 1,3-butanedoil, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol diacetate, diethylene glycol and tetraethylene glycol.

Aside from triethylene glycol, the only other candidates worth considering from the above group were found to be tetraethylene glycol, diethylene glycol, 1,3-propanediol and diethylene glycol monobutyl ether. Table XXIX shows differences in lubricity found between these various additives and triethylene glycol when used in an otherwise identical formulation. A formulation using 5000 molecular weight methoxypolyethylene glycol has also been included in the table for comparison purposes. The preferred amount of the particular organic additive specified for each of the formulations in the table had been previously determined as that amount which provided minimum drag during the wiping operation from the wet to dry stages with paper toweling.

                                      TABLE XXI                                    __________________________________________________________________________            COMPARISON TESTS BETWEEN FORMULATIONS CONTAINING                                                                  Basic  90.8 g H.sub.2 O                     TRIETHYLENE GLYCOL AND OTHER SELECTED ORGANICS                                                                    Formulation:                                                                          2.35g isopropanol                                                              4.05g 1-propanol                                                               --g organic - see below                                                        0.364g                                                                         NH.sub.4 OH.sup.(p)                                                            -  0.011g Surfactant                                                           BA-77.sup.(b)                                  Lubricity               Test Surface: 24" × 18"                                                  Plate Glass                               Organic Amount                                                                              Wet to Nearly Dry                                                                          Lubricity   Residual Contamination                #   Additive                                                                               (Grams)                                                                             Stage       Dry Stage   (Clean Glass)                         __________________________________________________________________________     IA-5                                                                               Triethylene                                                                            0.158                                                                               Low Drag    Low Drag    none                                      Glycol                                                                     IB-5                                                                               Tetraethylene                                                                          0.163                                                                               Slightly more drag                                                                         Slightly more drag                                    Glycol       than IA-5   than IA-5   none                                  IC-10                                                                              Diethylene                                                                             0.27 Very nearly same                                                                           Considerably more                                     Glycol       drag as IA-5                                                                               drag than IA-5. Towel                                                                      none                                                               grabs glass surface                               ID-4                                                                               Diethylene                                                                             0.087                                                                               Noticeably more drag                                                                       Noticeably more drag                                  Glycol       than IA-5   than IA-5   none                                      Monobutyl                                                                      Ether                                                                      IE-7                                                                               1,3-propane-                                                                           0.242                                                                               Same or slightly                                                                           Considerably more drag                                diol         less drag than IA-5                                                                        than IA-5. Towel grabs                                                                     none                                                               glass like ID-10                                  II-4                                                                               Polyethylene                                                                           0.202                                                                               Slightly more drag                                                                         Slightly less drag than                               Glycol       than IA-5 but a                                                                            IA-5. Definately less                                                                      none                                      PEG-6000.sup.(h)                                                                            little less than                                                                           drag after long                                                    IB-5        additional drying time                            __________________________________________________________________________      FOR NOTESSEE TABLE I                                                     

Table XXIX shows that the formulations containing diethylene glycol monobutyl ether had relatively poor drag characteristics, both during the wet to nearly dry and in the dry wiping stages. The 1,3-propanediol had low drag during the wet to nearly dry stages but then showed considerable drag when fully dry.

While the tetraethylene glycol was found to provide good lubricity throughout the entire wiping stages, it still did not provide as good overall lubricity as the triethylene glycol. In addition, tetraethylene glycol has been found to provide poorer overall lubricity than the higher (2000-20,000) molecular weight poly and alkoxypolyethylene glycols. Such a comparison can be made in Table XXIX by referring to the formulation containing the 6000 molecular weight polyethylene glycol.

For further reasons, tetraethylene glycol has been found to be a poor choice for cleaner solutions over that of triethylene glycol. This involves its slower evaporation rate (vapor pressure >0.001 mm at 20° C. and boiling point of 287.2° C.) which results in a residual glycol film remaining on the glass or other surface for considerably longer time periods than required. This is especially true when, through misuse, areas may not be completely wiped free of the cleaning solution. Combinations of the tri- and tetraethylene glycol were also evaluated but no advantage in doing so could be found.

In an attempt to further optimize the overall lubricity and cleaning properties of the triethylene glycol type compositions, it was decided to use formulation KB-14 as shown in Table XXV and XXVII. This formulation was chosen because it contains additional lubricity and grease cutting aids not present in the formulations of Table XXIX. This formulation was, of course, modified by replacing the 5000 molecular weight methoxypolyethylene glycol with an appropriate amount of triethylene glycol.

                                      TABLE XXX                                    __________________________________________________________________________             VARIATIONS OF BORATE AND PHOSPHATE ADDITIVES                                                                     Basic  86.75 g H.sub.2 O                     TO TRIETHYLENE GLYCOL CONTAINING FORMULATION                                                                     Formulation:                                                                          9.45 g isopropanol                                                             0.245g 1-propanol                                                              0.158g triethylene                                                             glycol                                                                         0.033g 2,3-butanediol                                                          0.08 g                                                                         NH.sub.4 HCO.sub.3                                                             -- g borate or                                                                 phosphate-                                                                     see below                                                                      0.156g                                                                         NH.sub.4 OH.sup.(p)                                                            0.012g Surfactant                                                              BX-78.sup.(c)                                   Test Surface: 24" × 18" Plate Glass                        Borate or                                                                               Amount                                                                              Lubricity        Lubricity                                   #   Phosphate                                                                               (Grams)                                                                             Wet to Nearly Dry Stage                                                                         Dry Stage                                   __________________________________________________________________________     MD-1                                                                               Na.sub.3 PO.sub.4 . 12H.sub.2 O                                                         0.1  Excellent - very low drag                                                                       Excellent - low drag                        MD-10                                                                              KBO.sub.2 . xH.sub.2 O                                                                  0.1  ˜MD-1 - very low drag                                                                     Slightly more drag than MD-1 but quite                                         low                                                                            drag                                        MD-9                                                                               K.sub.2 B.sub.4 O.sub.7 . 4H.sub.2 O                                                    0.1  Slightly more drag than MD-10                                                                   Slightly more drag than MD-10               MD-2                                                                               K.sub.3 PO.sub.4 . xH.sub.2 O                                                           0.1  Noticeably more drag than MD-1                                                                  ˜ MD-1                                MD-3                                                                               Na.sub.4 P.sub.2 O.sub.7 . 10H.sub.2 O                                                  0.1  Considerabe drag when almost dry                                                                Considerable drag                           MD-4                                                                               K.sub.4 P.sub.2 O.sub.7 . 3H.sub.2 O                                                    0.1  ˜MD-3      Slightly more drag than MD-3                MD-5                                                                               Na.sub.5 P.sub.3 O.sub.10                                                               0.1  Noticeably more drag than MD-1                                                                  ˜MD-3                                                   but less than MD-3                                           MD-6                                                                               K.sub.5 P.sub.3 O.sub.10                                                                0.1  ˜MD-4      ˜MD-4                                 MD-7                                                                               (NaPO.sub.3).sub.6                                                                      0.1  Noticeably more drag than MD-1                                                                  Noticeably more drag than MD-1 but                                             slightly                                                      but slightly less than MD-3                                                                     less than MD-3                              MD-8                                                                               Na.sub.2 B.sub.4 O.sub.7 . 10H.sub.2 O                                                  0.1  Noticeably more drag than MD-9                                                                  Considerable drag ˜MD-3               __________________________________________________________________________      *FOR NOTES  SEE TABLE I                                                  

Tests were then made by replacing the potassium tetroborate (K₂ B₄ O₇.4H₂ O) in the modified KB-14 formulation with a variety of other borates and phosphates. The results of this test are shown in Table XXX. The trisodium phosphate (Na₃ PO₄.12H₂ O) was found to be the preferred oil and grease cutting additive for these triethylene glycol containing formulations. Potassium metaborate (KBO₂.xH₂ O) and potassium tetraborate (K₂ B₄ O₇.4H₂ O) were also found to be good choices. Amounts of about 0.1 g of the phosphate or borate per 100 g of cleaner solution were used in the formulations of Table XXX but prior testing has shown that the amount used is not especially critical so long as noticeable residual deposits do not result.

Additional modifications were made in the triethylene glycol modified KB-14 formulation by replacing the 2,3-butanediol with other high boiling point organics. These included 1,3-propanediol, 3-methoxybutanol, diethylene glycol, monobutyl ether, 1,4-butanediol and 1,5-pentanediol. Amounts were adjusted for maximum lubricity properties in each instance. The 2,3-butanediol was found in these tests to provide the best overall lubricity although some of the others were found to give good results.

Table XXXI shows the effect on lubricity of varying the amount of 2,3-butanediol in a modified KB-14 type formulation containing triethylene glycol and trisodium phosphate. This data verified that the preferred amount of 2,3-butanediol was more than that required in the methoxypolyethylene glycol KB-14 formulation of the copending application.

The amount of triethylene glycol required for obtaining the highest lubricity and best overall cleaning properties had been determined earlier using formulations similar to that of IA-5 listed in Table XXIX. This determination was made again using the triethylene glycol modified KB-14 type formulation and also using the preferred 2,3-butanediol amount and the trisodium phosphate as the grease cutting additive. The results are shown in Table XXXII and indicate that the preferred amount of triethylene glycol has not changed. See formulation MB-5.

A formulation using 5000 molecular weight methoxypolyethylene glycol is also included in Table XXXII for comparison purposes--see formulation MB-7. Note that the amount of 2,3-butanediol has been increased in this one formulation to provide for maximum lubricity characteristics with a methoxypolyethylene glycol type system, in order to allow the best possible comparisons. Overall, both the triethylene glycol and methoxypolyethylene glycol formulations, MB-5 and MB-7, showed essentially equivalent lubricity and oil removal test results. In addition, Table XXXII includes a commercially available Window Glass and Chrome Cleaner, WINDEX, which shows somewhat greater overall drag properties during the wiping from wet to dry and dry stages and shows considerably more residual oil contamination in comparison to the triethylene glycol and methoxypolyethylene glycol formulations MB-5 and MB-7.

                                      TABLE XXXI                                   __________________________________________________________________________             VARIATIONS IN AMOUNT OF 2,3-BUTANEDIOL USING                                                                   Basic  86.75 g H.sub.2 O                       TRIETHYLENE GLYCOL CONTAINING FORMULATION                                                                      Formulation:                                                                          9.45 g isopropanol                                                             0.245g 1-propanol                                                              0.158g triethylene glycol                                                      --g 2,3-butanediol -                                                           see below                                                                      0.08g NH.sub.4 HCO.sub.3                                                       0.1g Na.sub.3 PO.sub.4 .                                                       12H.sub.2 O                                                                    0.156g NH.sub.4 OH.sup.(p)                                                     0.012g Surfactant                                                              BX-78.sup.(c)                                              Test Surface: 24" × 18" Plate Glass                2,3-Butanediol                                                                          Lubricity    Lubricity                                           #    Amount (Grams)                                                                          Wet to Nearly Dry Stage                                                                     Dry Stage                                           __________________________________________________________________________     MC-1 0.026    Noticeably more drag                                                                        ˜MC-11/4                                                    than MC-11/4                                                     MC-11/4                                                                             0.033    Excellent - very low drag                                                                   Excellent - low drag                                MC-11/2                                                                             0.039    Low drag but slightly                                                                       ˜MC-11/4                                                    more than MC-11/4                                                MC-13/4                                                                             0.046    Noticeably more drag than                                                                   ˜MC-11/4                                                    MC-11/4                                                          MC-2 0.052    Very noticeable drag-                                                                       ˜MC-11/4                                                    considerably more than                                                         MC-11/4                                                          __________________________________________________________________________      * FOR NOTES  SEE TABLE I                                                 

                                      TABLE XXXII                                  __________________________________________________________________________             VARIATIONS IN AMOUNTS OF TRIETHYLENE GLYCOL                                                                    Basic  86.75 g H.sub.2 O                       USING MODIFIED KB-14 FORMULATIONS                                                                              Formulation:                                                                          9.45 g isopropanol                                                             0.245g 1-propanol                                                              --g glycol - see below                                                         --g 2,3-butanediol - see                                                       below                                                                          0.08 g NH.sub.4 HCO.sub.3                                                      0.1 g Na.sub.3 PO.sub.4 .                                                      12H.sub.2 O                                                                    0.156g NH.sub.4 OH.sup.(p)                                                     0.012g Surfactant                                                              BX-78.sup.(c)                                Amount                                                                              2,3-Butanediol                                                                        Lubricity           Oil Removal Test                  #     Glycol (Grams)                                                                             Amt. (Grams)                                                                          Wet to Dry Stages   (1 Drop WESSON                    __________________________________________________________________________                                                  OIL)                              MB-2  Triethylene                                                                           0.063                                                                               0.033  Very great drag-not a good                                                                         Not Measured                            Glycol             formulation                                           MB-4  Triethylene                                                                           0.126                                                                               0.033  Very noticeably less drag than                                                                     Not Measured                            Glycol             MB-2 but very noticeably more                                                  drag than MB-5 below                                  MB-   Triethylene                                                                           0.142                                                                               0.033  Low drag-a little more drag than                                                                   Not Measured                      41/2  Glycol             MB-5 but noticeably less drag                                                  than MB-4                                             MB-5  Triethylene                                                                           0.158                                                                               0.033  Excellent-very low drag wet to                                                                     No visible oil streaks                  Glycol             nearly dry and when wiped to                                                   dry stage                                             MB-   Triethylene                                                                           0.173                                                                               0.033  Low drag-a little more drag than                                                                   Not Measured                      51/2  Glycol             MB-5 but noticeably less than                                                  MB-6 below                                            MB-6  Triethylene                                                                           0.189                                                                               0.033  Very Noticeably more drag than                                                                     Not Measured                            Glycol             MB-5 and slightly more than MB-4                      MB-7  Methoxy                                                                               0.2  0.026  Excellent-probably very slightly                                                                   No visible oil streaks,                                                        ˜MB-5                             Polyethylene       more drag in nearly dry state than                          Glycol -           MB-5 but probably very slightly less                        MPEG-5K.sup.(f)    drag than MB-5 when first reaching                                             dry stage. Definitely less drag than                                           MB-5 after extended drying time however               WINDEX       --   --     More drag definitely noticeably in                                                                 Many visible oil streaks                                                       over                                                       to nearly dry and in dry wiping                                                                    most of surface                                            than MB-5 or MB-7 above                               __________________________________________________________________________      FOR NOTES SEE TABLE I                                                    

In summary, the triethylene glycol has been found to supply a unique set of properties not found in any other organic compound tested as a substitute for the poly or alkoxypolyethylene glycols. It has been found to be a highly effective lubricant during the wiping from the wet to nearly dry stages and evaporates just slowly enough to provide very low surface drag even when wiped to the completely dry stage. It has also been found to provide highly effective oil and grease transfer from contaminated surfaces to the toweling during use.

Tests have further shown that properly adjusted triethylene glycol containing cleaner formulations can perform equally as well as their poly or alkoxypolyethylene glycol counterparts covered in my copending application. This applies to overall lubricity and ease of use as well as oil and grease removal and general cleaning characteristics. The primary differences between the two systems are that the higher molecular weight glycols provide long term recontamination protection but can, with careless or improper use, leave visual streaking on the surface being cleaned. On the other hand, the triethylene glycol system essentially eliminates the visual residue problem because of the rapid glycol evaporation but does not, of course, provide for long term recontamination protection.

Again, all test procedures used in evaluating the triethylene glycol containing formulations covered in Tables XXIX through XXXII were the same as those employed in the copending application. 

What is claimed:
 1. A water based cleaning composition consisting essentially of water on the order of about 59.3 to about 99.58 weight percent, a cleaning agent selected from the group consisting of ammonium hydroxide, a monohydroxy alcohol containing not more than 3 carbon atoms and mixtures thereof on the order of about 0.31 to about 40.3 weight percent plus an amount of a lubricity compound comprised of a water soluble alkyl derivative of ethylene glycol having the formula ROCH₂ (CH₂ OCH₂)_(n) CH₂ OR wherein n is at least 2 and R is an on the order of about 0.025 to about 0.3 weight percent to impart substantial lubricity to the composition. 